TWI600693B - White photosensitive resin composition, white hardened film, method for manufacturing white pattern - Google Patents

Description

White photosensitive resin composition, white cured film, white pattern Production method

The present invention relates to a white photosensitive resin composition, a white cured film using the same, a white pattern, and a method for producing the same.

The printed wiring board is usually formed by etching and removing unnecessary portions of the copper foil bonded to the laminated board to form circuit wiring, and the electronic component is placed at a predetermined portion by soldering. When such a printed wiring board is produced, a solder resist film is used. That is, the solder resist film is used as a protective film for a circuit when soldering an electronic component. The solder resist prevents solder from adhering to unnecessary portions during soldering and prevents the circuit conductor from being directly exposed to the air to react with oxygen or moisture content. Furthermore, it also functions as a permanent protective film of a circuit board. Therefore, various properties such as adhesion, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance are required.

In particular, it is required to be discolored from white at a high temperature when exposed to reflow solder or when irradiated with light.

For example, Patent Document 1 discloses a white photosensitive resin composition which uses a threne blue dye to obtain a cured product which suppresses discoloration caused by a heat history, but requires a coloring agent to be added. And there is a problem with the resolution of the pattern.

The printed wiring board is continually promoting miniaturization (fineness), multi-layering, and one board to achieve high density, and the mounting method is also progressing toward surface mounting technology (SMT). Therefore, for solder resist films, the requirements for refinement, high resolution, high precision, and high reliability are also increasing.

As a technique for forming such a solder resist pattern, a photoresist method capable of accurately forming a fine pattern has become a mainstream, and in particular, an alkali development type resist method has become mainstream.

For example, Patent Document 2 discloses a white photosensitive resin composition using an oxime ester photopolymerization initiator, and it is described that a pattern latent image can be accurately formed, but coloring resistance is exhibited. There are problems in the aspect.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-150461

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-134621

The present invention has been made in view of the above problems in the prior art, and an object thereof is to provide a white photosensitive resin composition, a white cured film, a white pattern, and a method for producing the same, wherein the white photosensitive resin composition can be formed even if heated (for example, A white cured film having a fine pattern such as a hole pattern having a pore diameter of 50 μm or less and having a color diameter of 50 μm or less is also less likely to occur at 265 ° C for 15 minutes.

The specific means for solving the above problems are as follows.

<1> A white photosensitive resin composition comprising (A) a binder polymer, (B) a polymerizable monomer, (C) a polymerization initiator, (D) a titanium dioxide particle having an average particle diameter of 100 nm or more and (E) a coloring preventing agent.

<2> The white photosensitive resin composition as described in <1>, wherein the titanium dioxide (D) has an average particle diameter of 180 nm or more.

<3> The white photosensitive resin composition as described in <1>, wherein the content of the titanium dioxide (D) in the solid content of the white photosensitive resin composition is 35 mass% or more.

The white photosensitive resin composition as described in any one of <1> to <3>, wherein the coloring inhibitor (E) is a phenol compound.

The white photosensitive resin composition as described in any one of <1> to <4> wherein the coloring inhibitor (E) has a substituent at ortho position to a phenolic hydroxyl group. Phenolic compound.

<6> The white photosensitive resin composition as described in any one of <1> to <5> further containing a dispersing agent, and in the solid component of the white photosensitive resin composition, the binder polymer (A) The total content of the above dispersant is 24% by mass or more and 46% by mass or less.

<7> A white photosensitive resin composition as described in <6>, which is white In the solid content of the photosensitive resin composition, the total content of the binder polymer (A) and the dispersant is 30% by mass or more and 46% by mass or less.

<8> The white photosensitive resin composition as described in <6>, wherein the dispersing agent is a polymer dispersing agent having an adsorption site.

<9> The white photosensitive resin composition as described in <8>, wherein the adsorption site is an acid-based adsorption site.

The white photosensitive resin composition as described in <9>, wherein the acid-based adsorption site is at least one of a phosphorus atom-containing group or a carboxylic acid group.

The white photosensitive resin composition as described in <10>, wherein the polymer dispersing agent is a polymer dispersing agent having a group containing a phosphorus atom as an acid-based adsorption site, and the polymer dispersing agent is a polymer dispersing agent. SOLSPERSE 26000, SOLSPERSE 36000 or SOLSPERSE 41000 (both manufactured by Lubrizol).

<12> The white photosensitive resin composition as described in <8>, wherein the polymer dispersing agent is represented by the following general formula (1).

In the above formula (1), R ¹ represents a (m+n) valent linking group, R ² represents a single bond or a divalent linking group; A ¹ represents a monovalent substituent, and the above monovalent substituent has At least one group selected from the group consisting of an acid group, a urea group, a urethane group, and a coordinating oxygen atom (coordinating) a group of an oxygen atom), a group containing a basic nitrogen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonium group Sulfonamide group, heterocyclic group, alkoxysilyl group, epoxy group, isocyanate group and hydroxyl group; n A ¹ And R ² may be the same or different, m represents a positive number of 8 or less, n represents 1 to 9, m+n satisfies 3 to 10; P ¹ represents a polymer chain; m P ¹ may be the same or different.

The white light-sensitive resin composition according to any one of the above-mentioned items (A), wherein the polymerization initiator (C) is an oxime ester compound represented by the following formula (A),

In the above formula (A), R ¹ , R ² and R ³ each independently represent a monovalent substituent.

<14> A white photosensitive resin composition comprising (A) a binder polymer, (B) a polymerizable monomer, (C) a polymerization initiator, (D) titanium oxide particles having an average particle diameter of 100 nm or more, and dispersion And the total content of the binder polymer (A) and the above dispersing agent is 24 in the solid content of the white photosensitive resin composition. The amount is %~46% by mass.

<15> The white photosensitive resin composition as described in <14>, wherein the total content of the binder polymer (A) and the dispersing agent is 30% by mass to 46 in the solid content of the white photosensitive resin composition. quality%.

The white photosensitive resin composition as described in any one of <1> to <15> which can be formed as a white cured film which has the color difference ΔE*ab of 3 or less before and after heating at 265 degreeC for 15 minutes.

The white photosensitive resin composition as described in any one of <1> to <16>, which can be formed as a white cured film having a color difference ΔE*ab of 2 or less before and after heating at 265 ° C for 15 minutes.

The white photosensitive resin composition as described in any one of <1> to <17> which can form the white hardening film which has the hole pattern of the pore diameter of 50 micrometers or less.

<19> A white cured film formed by using the white photosensitive resin composition as described in any one of <1> to <18>.

<20> A method of producing a white pattern, comprising the steps of: forming a white film by applying the white photosensitive resin composition according to any one of <1> to <18> on a substrate; a step of exposing the white film to the cover; and a step of developing the exposed white film to form a white pattern.

<21> A white pattern produced by the production method as described in <20>.

According to the present invention, a white photosensitive resin composition can be provided, white In the cured film, the white pattern, and the method for producing the same, the white photosensitive resin composition can be formed into a hole pattern having a pore diameter of 50 μm or less, which is not easily colored by heating (for example, at 265 ° C for 15 minutes). A finely patterned white cured film.

In the description of the group (atomic group) in the present specification, the substitution is not described. And the unsubstituted expression means a group (atomic group) containing no substituent, and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The description of the constituent elements described below may be performed according to a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, the numerical range represented by the "~" in this specification is a range which contains the numerical value of the [~~] and the numerical value as the lower-limit and upper-limit.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acryl" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene oxime. And methacryl oxime. In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present invention means a compound which is distinguished from an oligomer and a polymer and has a mass average molecular weight of 2,000 or less. In the present specification, the term "polymerizable compound" means a compound having a polymerizable group, which may be The monomer can also be a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

<White photosensitive resin composition>

The white photosensitive resin composition of the present invention contains (A) a binder polymer, (B) a polymerizable monomer, (C) a polymerization initiator, (D) titanium oxide particles having an average particle diameter of 100 nm or more, and (E) Anti-coloring agent. Thus, for example, a white cured film having a color difference ΔE ^* ab of 5 or less, preferably 3 or less, and having a pore pattern of 50 μm or less in a before and after heating at 265 ° C for 15 minutes can be formed.

The white photosensitive resin composition of the present invention can be formed even if added The heat (for example, at 265 ° C for 15 minutes) is also less likely to be colored, and a fine white pattern of a fine pattern having a pore diameter of 50 μm or less (preferably 40 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less) can be formed. Hereinafter, the performance of the white cured film having such a fine pattern may be simply referred to as "resolution".

The white photosensitive resin composition of the present invention preferably has a color difference ΔE ^* ab of 5 or less (preferably 3 or less, more preferably 2 or less, and particularly preferably 1 or less) before and after heating at 265 ° C for 15 minutes. White hardened film. Thereby, it is possible to prevent coloration such as yellowing of the white cured film.

The white photosensitive resin composition of the present invention is preferably a composition in which, when a white cured film having a film thickness of 4.0 μm is formed, the light transmittance in the thickness direction of the cured film is in the entire wavelength range of 400 nm to 700 nm. Less than 5% of the composition, more preferably less than 3% of the composition.

That is, in the white cured film of the present invention, when the film thickness is 4.0 μm, the light transmittance in the thickness direction of the film is in the entire wavelength range of 400 nm to 700 nm. It is less than 5%, more preferably less than 3%.

[(A) Binder Polymer]

The white photosensitive resin composition of the present invention contains a binder polymer from the viewpoint of improving film properties and the like.

The binder polymer preferably uses a linear organic polymer. Such a linear organic polymer can be used arbitrarily. It is preferred to select a linear or organic polymer which is soluble or swellable in water or weakly alkaline water for water development or weak alkaline water development. The linear organic polymer is selected for use not only as a film forming agent but also as a developer of water, weakly alkaline water or an organic solvent. For example, if a water-soluble organic polymer is used, water development can be performed. Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Laid-Open Publication No. SHO 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. a polymer, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, homopolymerizing or copolymerizing a monomer having an acid anhydride, and hydrolyzing or semi-esterifying or semi-aminating the acid anhydride unit. The resin is an epoxy acrylate which is obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include maleic anhydride.

Further, there is an acidic cellulose derivative having a carboxylic acid group in the side chain as well. Further, it is effectively used in the case of adding a cyclic acid anhydride to a polymer having a hydroxyl group.

In the present invention, when a copolymer is used as the binder polymer, the compound to be copolymerized may also use a monomer other than the monomers enumerated above. Examples of the other monomer include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, methacrylic acid-2 Acrylates and methacrylates having an aliphatic hydroxyl group such as hydroxypropyl ester, 3-hydroxypropyl methacrylate or 4-hydroxybutyl methacrylate.

(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid - 2-chloroethyl ester, glycidyl acrylate, 3,4-epoxycyclohexyl methacrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, An alkyl acrylate such as 2-allyloxyethyl acrylate or propargyl acrylate.

(3) Methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl ester, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate , 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenyl vinyl methacrylate, An alkyl methacrylate such as 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate or propargyl methacrylate.

(4) acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyl Ethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide , N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide, allyl methacrylamide, acrylamide or methacryl Guanamine.

(5) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, Vinyl ethers such as propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(7) Styrene such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene or p-ethoxylated styrene.

(8) A ketene such as methyl ketene, ethyl ketene, propyl ketene or phenyl ketene.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like.

(11) Maleic imine, N-propylene decyl acrylamide, N-acetyl methacrylamide, N-propyl methacrylamide, N-(p-chlorobenzoyl) Unsaturated quinone imine such as methacrylamide.

(12) A methacrylic monomer having a hetero atom bonded to the α-position. For example, the compounds described in each of the publications such as JP-A-2002-309057 and JP-A-2002-311569 can be cited.

In the present invention, the monomers are not particularly included within the scope of the present invention. A combination of restrictions can be applied to the synthesis of copolymers. For example, an example of a copolymer obtained by polymerizing a monomer component containing these monomers is shown below, but the present invention is not limited thereto. The composition ratio of the exemplified compounds shown below is mol%.

The above binder polymer preferably contains the following formula (ED) A repeating unit obtained by polymerizing a monomer component of a compound (hereinafter sometimes referred to as "ether dimer").

(In the formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent)

Thus, the white photosensitive resin composition of the present invention can form, for example, a white cured film which is excellent in coloring resistance when heated at 265 ° C for 15 minutes or the like. In the above formula (ED), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ^{2 in} the above-mentioned ether dimer is not particularly limited, and examples thereof include a methyl group and an ethyl group. a linear or branched alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl or 2-ethylhexyl; benzene An aryl group; an alicyclic group such as a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group or a 2-methyl-2-adamantyl group; An alkyl group substituted with an alkoxy group such as 1-methoxyethyl or 1-ethoxyethyl; an alkyl group substituted with an aryl group such as a benzyl group or the like. Among these groups, in particular, in terms of heat resistance, a substituent of a primary carbon or a secondary carbon which is not easily removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is preferable.

Specific examples of the ether dimer include Japanese Patent Laid-Open No. 2012-208494 Specific examples of the ether dimer described in the paragraph [0565] of the corresponding specification of the U.S. Patent Application Publication No. 2012/235099, the entire contents of which are incorporated herein by reference.

A specific example of the ether dimer is preferably 2,2'-[oxybis(methylene)]bis-2-acrylic acid dimethyl ester, 2,2'-[oxybis(methylene)]bis-2. - diethyl acrylate, 2,2'-[oxybis(methylene)]bis-2-cyclohexyl acrylate, 2,2'-[oxybis(methylene)]bis-2-acrylic acid Benzyl ester. These ether dimers may be used alone or in combination of two or more. Further, in the structure derived from the compound represented by the above formula (ED), other monomers may be copolymerized.

Examples of the other monomer copolymerizable with the ether dimer include a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, a monomer for introducing an epoxy group, and Other copolymerizable monomers other than the monomers. These monomers may be used alone or in combination of two or more.

Examples of the monomer for introducing an acid group include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, and a phenolic hydroxyl group such as N-hydroxyphenylmaleimide. Monomer, a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride. Among these monomers, (meth)acrylic acid is particularly preferred.

Further, the monomer for introducing an acid group may be a monomer which can impart an acid group after polymerization, and examples thereof include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and (meth) A monomer having an epoxy group such as a glycidyl acrylate or a monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate. In the case of using a monomer which can impart an acid group after polymerization, treatment for imparting an acid group after polymerization can be required. The treatment for imparting an acid group after the polymerization differs depending on the kind of the monomer, and examples thereof include the following treatments. In the case of using a monomer having a hydroxyl group, for example, a treatment of adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amine group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol may be added, or addition For example, a hydroxyl group produced by an acid such as (meth)acrylic acid is added to an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride. In the case of using a monomer having an isocyanate group, for example, a treatment of a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

Polymerizing a monomer component containing a compound represented by the general formula (ED) When the formed polymer contains a monomer for introducing an acid group, the content ratio of the monomer for introducing an acid group is not particularly limited, and among all the monomer components, it is preferably 5% by mass to 70% by mass. %, more preferably 10% by mass to 60% by mass.

Examples of the monomer for introducing a radical polymerizable double bond include (meth) a monomer having a carboxyl group such as acrylic acid or itaconic acid; maleic anhydride, itaconic anhydride, etc. a carboxylic anhydride group-containing monomer; (meth)acrylic acid glycidyl ester, (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester, o- (or m- or p-)vinylbenzyl glycidyl ether, etc. A monomer such as an epoxy group. When a monomer for introducing a radically polymerizable double bond is used, it is necessary to carry out a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting a radically polymerizable double bond after the polymerization differs depending on the type of the monomer capable of imparting a radical polymerizable double bond, and examples thereof include the following treatments. When a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid is used, an addition of glycidyl (meth)acrylate or a 3,4-epoxycyclohexyl (meth)acrylate may be mentioned. Treatment of a compound having an epoxy group and a radical polymerizable double bond such as a methyl ester, o- (or m- or p-) vinylbenzyl glycidyl ether. When a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth)acrylate may be added. Processing. If using glycidyl (meth)acrylate, -3,4-epoxycyclohexylmethyl (meth)acrylate, o- (or m- or p-) vinylbenzyl glycidyl ether, etc. In the case of a monomer, a treatment of a compound having an acid group and a radical polymerizable double bond such as (meth)acrylic acid may be mentioned.

Polymerizing a monomer component containing a compound represented by the general formula (ED) When the formed polymer contains a monomer for introducing a radically polymerizable double bond, the content ratio of the monomer for introducing the radical polymerizable double bond is not particularly limited, and among all the monomer components, Preferably, it is 5 mass% to 70 mass%, more preferably 10 mass% to 60 mass%.

Examples of the monomer for introducing an epoxy group include (meth)acrylic acid shrinkage. A glyceride, a 3,4-epoxycyclohexylmethyl (meth)acrylate, an o- (or m- or p-) vinylbenzyl glycidyl ether, and the like.

In the case where the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an epoxy group, the content ratio of the monomer for introducing the epoxy group is It is not particularly limited, and is preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 60% by mass based on all the monomer components.

Examples of other copolymerizable monomers include methyl (meth)acrylate, Ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Tributyl ester, methyl 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. (methyl) Acrylates; aromatic vinyl compounds such as styrene, vinyl toluene, and α-methylstyrene; N-substituted maleates such as N-phenylmaleimide and N-cyclohexylmaleimide Imines; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl esters such as vinyl acetate Wait. Among these monomers, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and benzene are preferred in terms of good transparency and resistance to heat resistance. Ethylene.

Polymerizing a monomer component containing a compound represented by the general formula (ED) When the formed polymer contains another copolymerizable monomer, the content ratio of the other copolymerizable monomer is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less.

The weight average molecular weight of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, and the viscosity of the white photosensitive resin composition and the coating formed by the composition are not particularly limited. From the viewpoint of heat resistance of the film, it is preferably from 2,000 to 200,000, more preferably from 5,000 to 100,000, and still more preferably from 5,000 to 20,000.

In the case where the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) has an acid group, the acid value is preferably from 30 mgKOH/g to 500 mgKOH/g, more preferably 50 mgKOH/ G~400mgKOH/g is preferred.

Polymerization of a monomer component containing a compound represented by the general formula (ED) The polymer can be easily obtained by polymerizing the above monomer containing at least an ether dimer. At this time, the cyclization reaction of the ether dimer is carried out at the same time as the polymerization to form a tetrahydropyran ring structure.

The polymerization method to be used in the synthesis of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, and various conventionally known polymerization methods can be employed, and it is particularly preferred to use a solution polymerization method. . Specifically, for example, a polymerization method in which a monomer component containing a compound represented by the general formula (ED) is polymerized can be synthesized according to a method for synthesizing the polymer (a) described in JP-A-2004-300204. Things.

Hereinafter, the monomer containing the compound represented by the general formula (ED) is shown. Exemplary compounds of the polymer obtained by partial polymerization, but the present invention is not limited to these compounds. The composition ratio of the exemplified compounds shown below is mol%.

[Chemical 5]

In the present invention, it is especially preferred to make 2,2'-[oxybis(methylene)]bis-2-acrylic acid. Dimethyl ester (hereinafter referred to as "DM"), benzyl methacrylate (hereinafter referred to as "BzMA"), methyl methacrylate (hereinafter referred to as "MMA"), methacrylic acid (hereinafter referred to as "MAA") ), 2-hydroxypropanediol dimethacrylate (hereinafter referred to as "X") copolymerization The resulting polymer. Youjia is DM:BzMA:MMA:MAA:X has a molar ratio of 5~15:40~50:5~15:5~15:20~30. It is preferred that 95% by mass or more of the components constituting the copolymer used in the present invention are the components. Further, the weight average molecular weight of the polymer is preferably from 9000 to 20,000.

The polymer used in the present invention preferably has a weight average molecular weight (polystyrene equivalent value measured by Gel Permeation Chromatography (GPC) method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 ×10 ⁵ , and further preferably 5000~5×10 ⁴ .

A binder that can be used in the white photosensitive resin composition of the present invention The weight average molecular weight (polystyrene equivalent value measured by GPC method) of the compound is preferably 5,000 or more, more preferably 10,000 or more and 300,000 or less, and the number average molecular weight is preferably 1,000 or more, more preferably 2,000. Above, the range of 250,000 or less. The degree of dispersion (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.

The binder polymer may be any of a random polymer, a block polymer, a graft polymer, and the like.

The binder polymer which can be used in the present invention can be obtained by a previously known method. Method to synthesize. Examples of the solvent used in the synthesis include tetrahydrofuran, dichloroethylene, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 2-methoxyB. Acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N , N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl hydrazine, Water, etc. These solvents may be used alone or in combination of two or more.

The radical polymerization initiator used in the case of the binder polymer which can be used for the white photosensitive resin composition of the present invention is exemplified by a known compound such as an azo initiator or a peroxide initiator.

In the white photosensitive resin composition of the present invention, the binder polymer may be used alone or in combination of two or more.

The content of the binder polymer is preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 50% by mass or less, and further preferably 5% by mass based on the total solid content of the white photosensitive resin composition. % or more and 46% by mass or less, more preferably 20% by mass or more and 46% by mass or less, and particularly preferably 24% by mass or more and 46% by mass or less.

[(B) Polymerizable monomer]

(B) The polymerizable monomer is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, and more preferably has at least one, preferably two or more terminal ethylenically unsaturated bonds. compound of. Such compounds are widely known in the art, and the compounds can be used without particular limitation in the present invention.

Further, the (B) polymerizable monomer is also preferably a compound having an ethylenically unsaturated group having at least one vinyl group capable of undergoing addition polymerization and having a boiling point of 100 ° C or higher at normal pressure. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol III (Meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylol Propane tris(propylene methoxypropyl)ether, tris(propylene methoxyethyl) isocyanurate and a mixture of these compounds are preferably pentaerythritol tetra(meth)acrylate.

Among them, the polymerizable monomer or the like is preferably pentaerythritol tetraacrylate (commercially available as A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (commercially available as KAYARAD). D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercial product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (methyl) Acrylate (commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercial product is KAYARAD DPHA; It is more preferably pentaerythritol tetraacrylate.

The polymerizable monomer or the like may be a polyfunctional monomer and has an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, the ethylenic compound can be used as it is if it has an unreacted carboxyl group as described above, and if necessary, a non-aromatic carboxylic anhydride can be reacted with a hydroxyl group of the above-mentioned ethylenic compound to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated six. Hydrogen phthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an aliphatic polyhydroxy compound and The ester of an unsaturated carboxylic acid is preferably a polyfunctional monomer having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and particularly preferably an aliphatic polyhydroxy compound in the ester. Pentaerythritol and / or dipentaerythritol. For example, M-305, M-510, M-520, etc. of the Aronix series which are polyacid-modified acryl-type oligomers manufactured by the East Asia Synthetic Co., Ltd. are mentioned.

The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, and more preferably from 5 mg-KOH/g to 30 mg-KOH/g. In the case where a polyfunctional monomer having two or more acid groups is used in combination or a polyfunctional monomer having no acid group is used in combination, it is necessary to prepare in such a manner that the acid value of the entire polyfunctional monomer is within the above range.

Regarding the polymerizable monomers, their structures, used alone or in combination, and added The details of the method of use such as the amount can be arbitrarily set according to the final performance design of the white photosensitive resin composition. For example, it is selected according to the following points.

In terms of sensitivity, a structure having a large content of unsaturated groups per molecule is preferred, and in many cases, it is preferably a difunctional or higher. In addition, in order to increase the strength of the cured film, it is preferable to use a trifunctional or higher functional group, and further, the functional group is different and the polymerizable group is different (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound). The method of adjusting both sensitivity and intensity is also effective.

In addition, the compatibility and dispersibility of other components (for example, a polymerization initiator, titanium dioxide particles, and the like) contained in the white photosensitive resin composition, the selection and use of the polymerizable monomer are important factors. For example, compatibility may be improved by using a low-purity compound or using two or more other components in combination. In addition, it can also be A specific structure is selected by improving the adhesion to a hard surface such as a substrate.

The content of the (B) polymerizable monomer is preferably in the range of 1% by mass to 40% by mass, more preferably in the range of 3% by mass to 35% by mass, even more preferably based on the total solid content of the white photosensitive resin composition. It is in the range of 5 mass% to 30 mass%.

When the content of the (B) polymerizable monomer is within this range, coloring is prevented and the curability is good, which is preferable.

[(C) Polymerization initiator]

The white photosensitive resin composition of the present invention contains a polymerization initiator (C). Thereby the hardenability is improved.

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known polymerization initiators.

In addition, for the viewpoint of good hardening in the exposure step by radiation irradiation described later, for example, it is preferable to have a radiation-sensitive linearity to the visible light in the ultraviolet range. Further, it may be an active agent which generates a living radical by some action with a photo-excited sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer.

Further, the above polymerization initiator is preferably a compound containing at least one molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm, more preferably 330 nm to 500 nm.

The polymerization initiator is preferably an anthraquinone compound, more preferably an oxime ester compound.

Specific examples of the oxime-based initiators include the compounds described in JP-A-2001-233842, and the compounds described in JP-A-2000-80068. The compound described in JP-A-2006-342166.

In the present invention, an antimony derivative or the like which can be preferably used as a polymerization initiator Examples of the compound include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3-propoxyaniminobutane. 2-keto, 2-ethoxymethoxyiminopentan-3-one, 2-ethoxymethoxyimino-1-phenylpropan-1-one, 2-benzylideneoxyimine 1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane -1-ketone and the like.

The oxime ester compound can be listed as: "Journal of the Chemical Society, JCS) Perkin II (1979) pp. 1653-1660, "Journal of the Chemical Society (JCS) Perkin II (1979) Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Journal of Applied Polymer Science (2012) Pp. 725-731, Japanese Patent Publication No. 2000-66385, Japanese Patent Laid-Open Publication No. 2000-80068, Japanese Patent Publication No. 2004-534797, and Japanese Patent Laid-Open No. 2006-342166 The compounds and the like described in each of the publications.

Further, the following compounds may also be used as the oxime esterification other than the above description. A compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is incorporated in the N-position of the carbazole, and a compound described in US Pat. No. 7,626,957, the disclosure of which is incorporated herein by reference. Japanese Patent Laid-Open Publication No. 2010-15025, which incorporates a nitro group, and a US Patent Publication No. 2009-292039 The compound described in Japanese Laid-Open Patent Publication No. 2009-131189, the compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has maximum absorption at 405 nm and is The compound described in JP-A-2009-221114, which has a good sensitivity, is a g-ray source.

Further, a cyclic ruthenium compound described in JP-A-2007-2310 and JP-A-2007-322744 can be preferably used. Among the cyclic ruthenium compounds, the cyclic ruthenium compound which is condensed on the carbazole dye described in Japanese Patent Laid-Open Publication No. 2010-185072, and the like, has a high light absorbing property. High sensitivity can be achieved.

In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of the ruthenium compound, can regenerate the active radical by polymerizing an inactive radical, thereby achieving high sensitivity.

In addition, a ruthenium compound having a specific substituent disclosed in Japanese Laid-Open Patent Publication No. 2007-269779, or a ruthenium compound having a thioaryl group disclosed in JP-A-2009-191061, may be mentioned.

Among them, the polymerization initiator (C) is particularly preferably an oxime ester compound represented by the following formula (A).

[Chemistry 7]

In the above formula (A), R ¹ , R ² and R ³ each independently represent a monovalent substituent.

Further, the compound may be a ruthenium compound in which the N-O bond of ruthenium is (E), a ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

The monovalent substituent of R ¹ is not particularly limited, and examples thereof include an aryl group and a heterocyclic group. Additionally, the groups may have more than one further substituent.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Further examples of the substituent which the aryl group and the heterocyclic group of R ¹ may have include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a decyl group, an alkoxycarbonyl group, an amine group, and a hetero group. A ring group, a halogen atom, or the like.

Among them, R ^{1 is} particularly preferably a structure Sub-1 to Sub-11 shown below.

Further, in the group shown below, "*" indicates a bonding position with the carbonyl group Y in the above formula (A), and each group may have one or more further substituents. Further substituents are as described above.

[化8]

The monovalent substituent of R ² is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an alkynyl group, and preferably a carbon number of 1 to 12, more preferably an alkyl group. Additionally, the groups may have more than one further substituent.

Further substituents which the alkyl group, the cycloalkyl group and the alkynyl group of R ² may have include a hexyl group; further described above as a further substituent which the aryl group and the heterocyclic group of R ¹ may have. The substituent or the like is preferably an arylthio group, and the arylthio group as the further substituent is more preferably substituted or unsubstituted in terms of improving sensitivity and suppressing coloration caused by heating over time. The phenylthio group is preferably a structure shown below in terms of sensitivity. Further, Me represents a methyl group, and Et represents an ethyl group.

[Chemistry 9]

The monovalent substituent of R ³ is not particularly limited, and examples thereof include an alkyl group and an aryl group. Additionally, the groups may have more than one further substituent.

The alkyl group for R ³ may, for example, be an alkyl group as described above as a monovalent substituent for R ² .

The aryl group as described above for R ³ may be exemplified above as the monovalent substituent for R ¹ .

Further substituents which the alkyl group and the aryl group of R ³ may have include the above-mentioned further substituents which are described as further examples of the aryl group of R ¹ and the further substituent which the heterocyclic group may have.

Specific examples of the ruthenium compound which can be preferably used are shown below (PIox-1) ~ Specific example (PIox-13), but the present invention is not limited to these specific examples.

[化10]

Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and especially Iruka (or IRGACURE)-OXE01 (manufactured by BASF).

The ruthenium compound has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000.

The measurement of the molar absorption coefficient of the compound can be carried out by a known method. Specifically, for example, an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian Co., Ltd.) is preferably used, and an ethyl acetate solvent is used. The concentration was measured at a concentration of 0.01 g/L.

The polymerization initiator used in the present invention may also be used in combination as needed. More than one species.

Since the white photosensitive resin composition of the present invention is required to form a fine pattern in a sharp shape, it is important to be hardenability and develop the unexposed portion without leaving a residue.

From this point of view, it is especially preferred to use a hydrazine compound for the polymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, a stepper is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is required to suppress the addition amount of the polymerization initiator. It is low, and therefore, in consideration of these aspects, the (C) polymerization initiator is preferably a ruthenium compound when forming a fine pattern such as a solid photographic element.

The present invention is relative to the total solid content of the white photosensitive resin composition The content of the (C) polymerization initiator contained in the white photosensitive resin composition (the total content in the case of two or more kinds) is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more. 20% by mass or less, and more preferably 1% by mass or more, 15 The mass% or less is particularly preferably 3% by mass or more and 9% by mass or less. By setting it as this range, the problem of coloring does not arise, and favorable hardenability and pattern formation are acquired with favorable sensitivity. Further, since the white photosensitive resin composition of the present invention is not easily transmitted by light, it is preferred to add a polymerization initiator which is more than a usual photosensitive resin composition.

[(D) Titanium dioxide particles having an average particle diameter of 100 nm or more]

The titanium dioxide particles of the present invention may be represented by the chemical formula TiO ₂ , and preferably have a purity of 70% or more, more preferably 80% or more, and further preferably 85% or more. The lower titanium oxide or the titanium oxynitride represented by the general formula Ti _n O _2n-1 (n is a number of 2 to 4) is preferably 30% by mass or less, more preferably 20% by mass or less, and further Good is 15% by mass or less.

The titanium dioxide particles of the present invention are not particularly limited as long as the average particle diameter is 100 nm or more, and can be appropriately selected from commercially available titanium oxide particles, for example.

The average particle diameter (number average particle diameter) of the titanium dioxide particles is 100 nm or more, preferably 180 nm or more. When the average particle diameter of the titanium dioxide particles is less than 100 nm, the reflectance may be lowered.

The upper limit of the average particle diameter of the titanium dioxide particles is not particularly limited, but is preferably 1000 nm or less, more preferably 500 nm or less.

The average particle diameter of the titanium dioxide particles in the present invention means a value obtained by diluting a mixed liquid or dispersion containing titanium oxide particles to 80 times by using propylene glycol monomethyl ether acetate, and using the obtained diluent for dynamic use. The light scattering method was used for the measurement.

In this measurement, the average particle diameter of the titanium dioxide particles is set to use the daily machine stock The number average particle size obtained from Microtrac UPA-EX150 manufactured by Ltd.

In the present invention, the refractive index of the titanium dioxide particles is not particularly limited, and from the viewpoint of obtaining a high refractive index, it is preferably 1.75 to 2.70, more preferably 1.90 to 2.70.

Further, the specific surface area of the titanium oxide particles is preferably from 10 m ² /g to 400 m ² /g, more preferably from 10 m ² /g to 200 m ² /g, further preferably from 10 m ² /g to 150 m ² /g, most preferably 10 m ² /g~40m ² /g.

Further, the shape of the titanium dioxide particles is not particularly limited. For example, it may be in the form of rice grains, spheres, cubes, spindles or indefinite shapes.

The titanium dioxide particles of the present invention may also be surface treated by an organic compound. Examples of the organic compound used in the surface treatment include a polyol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. Among them, a decane coupling agent is preferred. Further, the titanium dioxide particles of the present invention are preferably treated with Al (aluminum), Si (antimony), and an organic substance.

The surface treatment can be carried out by using a single surface treatment agent, or can be carried out by combining two or more surface treatment agents.

Further, the surface of the titanium oxide particles is preferably covered with an oxide of aluminum, lanthanum, zirconium or the like. Thereby, the weather resistance is further improved.

A commercially available product can be preferably used for the titanium dioxide particles of the present invention.

Commercially available products of titanium dioxide particles include, for example, Tipaque R-550, Tipaque R-580, Tipaque R-630, and Taipak (trade name) manufactured by Ishihara Sangyo Co., Ltd. Tipaque) R-670, Tipaque R-680, Tipaque R-780, Tipaque R-780-2, Tipaque R-820, Tipaque R-830, Tipaque R-850, Tipaque R-855, Tipaque R-930, Tipaque R-980, Tipaque CR-50, Tipaque CR-50-2, Tipaque CR-57, Tipaque CR-58, Tipaque CR-58 - 2, Tipaque CR-60, Tipaque CR-60-2, Tipaque CR-63, Tipaque CR-67, Tipaque CR-Super70, Tipaque CR-80, Tipaque CR-85, Tipaque CR-90, Tipaque CR-90-2, Tipaque CR-93, Taipak (Tipaque) Tipaque) CR-95, Tipaque CR-953, Tipaque CR-97, Tipaque PF-736, Tipaque PF-737, Tipaque PF-742 , Tipaque PF-690, Tipaque PF-691, Tipaque PF-711, Tipaque PF-739, Tipaque PF-740, Tipaque ) PC-3, Tipaque S-305, Tipaque CR-EL, Tipaque PT-301, Tipaque PT-501A, Tipa Que) PT-501R, manufactured by 堺Chemical Industries Co., Ltd. under the trade names R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44, R-45M, R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR-52, manufactured by Tayca Co., Ltd. The trade names are JR, JRNC, JR-301, JR-403, JR-405, JR-600A, JR-600E, JR-603, JR-605, JR-701, JR-800, JR-805, JR- 806, JR-1000 Those who are manufactured by Titanium Industry Co., Ltd. under the trade names of KR-310, KR-380, and KR-380N are manufactured by Fuji Titanium Industrial Co., Ltd. under the trade names of TR-600, TR-700, TR-750, TR-. 840, TR-900, etc., preferably Tipaque CR-90-2.

In the present invention, the titanium oxide particles (D) may be used alone or in combination of two or more.

The content of the titanium oxide particles in the white photosensitive resin composition of the present invention is preferably 30% by mass or more, and more preferably 35% by mass or more based on the total solid content of the white photosensitive resin composition.

The upper limit of the content is not particularly limited, and is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 70% by mass or less, and most preferably 60% by mass based on the total solid content of the white photosensitive resin composition. %the following.

[Dispersant]

The white photosensitive resin composition of the present invention preferably contains a dispersant, and more preferably contains a polymer dispersant having an adsorption site, from the viewpoint of improving the dispersibility of the titanium oxide particles (D) in the composition.

In the present invention, the sites having the adsorption ability to the titanium oxide particles (D) are collectively referred to as "adsorption sites" as appropriate.

The adsorption site of the present invention may be exemplified by having at least one selected from the group consisting of the following groups a monovalent substituent of a group in the resulting group, etc.: an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group containing a basic nitrogen atom, a heterocyclic group An alkoxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group.

Examples of the above-mentioned "acid group" include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphorus atom-containing group (phosphoric acid group, monophosphate group, polyphosphate group, etc.) and a boric acid group. More preferably, it is a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphorus atom-containing group (phosphoric acid group, monophosphate group, polyphosphate group, etc.), and particularly preferably a carboxylic acid group or a phosphorus atom-containing group. group.

Examples of the "ureido group" include -NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein, R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 or more carbon atoms). Or an aralkyl group having a carbon number of 7 or more is more preferably -NR ¹⁵ CONHR ¹⁷ (wherein, R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, carbon number 6 or more aryl groups and aralkyl groups having 7 or more carbon atoms are particularly preferably -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or carbon). Number 7 or more of aralkyl groups).

Examples of the above-mentioned "urethane group" include -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , and -OCONR ²² R ²³ (here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and the like, and more preferably -NHCOOR ¹⁸ or -OCONHR ²¹ (this) In addition, R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms, and more preferably -NHCOOR ¹⁸ or -OCONHR ²¹ ( Here, R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

Examples of the "group containing a coordinating oxygen atom" include an acetoacetone group and a crown ether.

Further, examples of the "basic group containing a basic nitrogen atom" include an amine group (-NH ₂ ) and a substituted imine group (-NHR ⁸ , -NR ⁹ R ¹⁰ , here, R ⁸ and R ⁹ and R ¹⁰ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms, and an indenyl group represented by the following formula (a1), and the following formula (a2) The amidinyl or the like represented is a preferred example.

In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

More preferably, these groups are an amine group (-NH ₂ ), a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ and R ¹⁰ each independently represent carbon The alkyl group represented by the above formula (a1), wherein R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms, in the formula (a1), Phenyl group, benzyl group, and fluorenyl group represented by the above formula (a2). In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group, and the like.

In particular, an amine group (-NH ₂ ), a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ independently represent a carbon number of 1 to 1 may be preferably used. In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, and an alkyl group represented by the above formula (a1). Benzyl], a fluorenyl group represented by the above formula (a2). In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group, and the like.

The alkyl group in the above "alkoxycarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group and an ethyl group.

The alkyl group in the above "alkylaminocarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.

The "carboxylate group" may, for example, be a group containing an ammonium salt of a carboxylic acid.

The "sulfonamide group" may be substituted with a hydrogen atom bonded to a nitrogen atom via an alkyl group (methyl group, etc.), a mercapto group (ethyl fluorenyl group, a trifluoroethenyl group or the like).

The above "heterocyclic structure" may, for example, be exemplified by the following structure: a thiophene Phenanthrene, furan, dibenzopyran, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazole, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadipine Azole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoporphyrin, isoindolinone, benzimidazolone , benzothiazole, amber imine, phthalimide, naphthyl imine, etc., hydrazine, hydantoin, quinone, quinoline, carbazole, acridine, Acridone, hydrazine.

Furthermore, the above "heterocyclic structure" may further have a substituent, and the substituent may be further substituted. For example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, and an N-sulfonium group are mentioned. Alkoxy groups such as an amine group and an ethoxy group having 1 to 6 carbon atoms; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group or an ethoxy group; a halogen atom such as chlorine or bromine; a methoxycarbonyl group and an ethoxy group; Alkoxycarbonyl group having 2 to 7 carbon atoms such as a carbonyl group or a cyclohexyloxycarbonyl group, a carbonate group such as a cyano group or a third butyl carbonate.

The above "alkoxyalkylene group" may be a monoalkoxyalkylene group or a dialkoxy group. Any one of a decyl group and a trialkoxyalkyl group is preferably a trialkoxyalkylene group, and examples thereof include a trimethoxydecyl group and a triethoxydecyl group.

The above "epoxy group" may, for example, be a substituted or unsubstituted oxiranyl group (oxyethylene group).

The adsorption site is preferably an acid adsorption site. Examples of the acid-based adsorption site include an acid group and the like. Among them, it is preferred that the acid-based adsorption site is at least one of a phosphorus atom-containing group or a carboxylic acid group.

In the present invention, the polymer dispersant having the above-mentioned adsorption site is preferably a polymer dispersant represented by the following formula (1).

In the above formula (1), R ¹ represents a (m+n)-valent linking group, and R ² represents a single bond or a divalent linking group.

A ¹ represents a monovalent substituent, and the above monovalent substituent has at least one group selected from the group consisting of an acid group, a urea group, a urethane group, and a coordinating oxygen atom. Group, a group containing a basic nitrogen atom, a heterocyclic group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, an alkoxyalkyl group, an epoxy group, an isocyanate group And hydroxyl. The n A ¹ and R ² may be the same or different.

m represents a positive number of 8 or less, n represents 1 to 9, and m+n satisfies 3 to 10.

P ¹ represents a polymer chain. m P ¹ may be the same or different.

The polymer compound represented by the above formula (1) can be referred to the description of paragraph 0039 of the Japanese Patent Application Laid-Open No. 2007-277514 (the corresponding US Patent Application Publication No. 2010/0233595 [0053]). These are incorporated into the specification of the present application.

Since the substituent A ¹ of the polymer dispersant represented by the above formula (1) can interact with the titania particles (D), the dispersant represented by the above formula (1) has n (1~) The 9 substituents A ¹ can strongly interact with the titanium dioxide particles (D). In addition, the m polymer chains P ¹ of the polymer dispersant represented by the above formula (1) can function as a steric repulsion group, and by having m, it can exhibit good steric repulsive force and make titanium dioxide. The particles (D) are uniformly dispersed. Further, it is presumed that the polymer dispersant represented by the above formula (1) does not cause agglomeration of particles due to cross-linking between particles which may occur in a dispersant having a previously grafted random structure in a molecular structure. Disadvantages.

Hereinafter, each group in the above formula (1) will be described in detail. again The polymer dispersant represented by the formula (1) is also disclosed in Japanese Patent Laid-Open No. Hei. No. 2007-277514 (Japanese Patent Application No. 2006-269707). The contents and preferred configurations can also be applied to the following description, and overlapping descriptions are omitted as appropriate.

The above A ¹ represents a monovalent substituent having a structure having at least one functional group having an adsorption ability for the titanium oxide particles (D), and a structure having an adsorption ability to the titanium oxide particles (D), such as a heterocyclic structure.

Further, the portion (the functional group and the structure) having the adsorption ability to the titanium oxide particles (D) corresponds to the above-mentioned "adsorption site".

The adsorption site may contain at least one of A ¹ and may contain two or more types.

With respect to A ¹ having at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group containing a basic nitrogen atom, a heterocyclic group, an alkoxycarbonyl group Details of the monovalent substituent of the group in the group consisting of an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group, such as As the adsorption site, as having at least one selected from the group consisting of an acid group, a ureido group, a urethane group, a group having a coordinating oxygen atom, a group containing a basic nitrogen atom, a heterocyclic group, or an alkane a monovalent substituent of a group in the group consisting of an oxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group. .

Further, in the present invention, the "monovalent substituent having at least one adsorption site" is the adsorption site and one to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, and 1 a monovalent substituent in which a linking group formed by ~400 hydrogen atoms and 0 to 40 sulfur atoms is bonded. Further, in the case where the adsorption site itself can constitute a monovalent substituent, the adsorption site itself can also be a monovalent substituent represented by A ¹ .

The linking group bonded to the adsorption site is preferably a single bond or one by one. a linking group formed by 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, the organic linking group may be unsubstituted It may also have a substituent.

In the above, the above A ¹ preferably has at least one group selected from the group consisting of an acid group, a urea group, a urethane group, a sulfonylamino group, a quinone imine group, and a group having a coordinating oxygen atom. A monovalent substituent of a group in a group.

In particular, A ^{1 is more} preferably a monovalent substitution having at least one functional group having a pKa of 5 to 14 from the viewpoint of improving the interaction with the titanium oxide particles (D), increasing the refractive index, and lowering the viscosity of the composition. base.

The term "pKa" as used herein refers to the definitions described in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.).

The functional group having a pKa of 5 to 14 may, for example, be a ureido group, a urethane group, a sulfonylamino group, a quinone imine group or a group containing a coordinating oxygen atom.

Specific examples thereof include a urea group (pKa of about 12 to 14), a urethane group (pKa of about 11 to 13), and a COCO ₂ CO- (a pKa of 8 as a coordinating oxygen atom). ~10 or so), sulfonamide group (pKa is about 9 to 11) and the like.

The above A ^{1 is} preferably represented by a monovalent substituent represented by the following formula (4).

In the above formula (4), B ¹ represents the above-mentioned adsorption site (i.e., acid group, urea group, urethane group, group containing a coordinating oxygen atom, a group containing a basic nitrogen atom, alkoxy group) Alkylcarbonyl, alkylaminocarbonyl, carboxylate, sulfonylamino, heterocyclyl, alkoxyalkyl, epoxy, isocyanate or hydroxy), R ²⁴ represents a single bond or (a+1) The link of the price. a represents an integer of 1 to 10, there are a number of B (4) in the general formula ¹ may be the same or different.

The adsorption site represented by the above B ¹ is the same as the adsorption site of A ¹ constituting the above formula (1), and preferred examples are also the same.

Among them, an acid group, a urea group, a urethane group, a sulfonylamino group, a quinone imine group or a group having a coordinating oxygen atom is preferred, and a functional group having a pKa of 5 to 14 is more preferred. From this point of view, a ureido group, a urethane group, a sulfonylamino group, a quinone imine group or a group containing a coordinating oxygen atom is more preferable.

R ²⁴ represents a single bond or a (a+1)-valent linking group, and a represents 1 to 10. Preferably, a is 1 to 7, more preferably a is 1 to 5, and particularly preferably a is 1 to 3.

The (a+1)-valent linking group includes from 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group formed may be unsubstituted or more substituted.

R ^{24 is} preferably a single bond or is formed by 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms. a (a+1)-valent linking group, more preferably a single bond or from 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and (a+1) valent linking group formed by 0 to 7 sulfur atoms, particularly preferably a single bond or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, A (a+1)-valent linking group formed by one to 30 hydrogen atoms and 0 to 5 sulfur atoms.

In the above, when the (a+1)-valent linking group has a substituent, Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amine group, a carboxyl group, and a sulfonylamino group. a sulfonylamino group, an ethoxy group having a carbon number of 1 to 6 such as a decyloxy group, a methoxy group such as a methoxy group and an alkoxy group having 1 to 6 carbon atoms, a halogen atom such as chlorine or bromine, and a methoxycarbonyl group. And an alkoxycarbonyl group having 2 to 7 carbon atoms such as an ethoxycarbonyl group or a cyclohexyloxycarbonyl group, a carbonate group such as a cyano group or a third butyl carbonate.

In the above formula (1), R ² represents a single bond or a divalent linking group. The n R ^{2 's} may be the same or different.

The divalent linking group includes a group formed by 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. It may be unsubstituted or substituted.

R ^{2 is} preferably a single bond or is formed by 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms. The divalent linking group is more preferably a single bond or from 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 The divalent linking group formed by the sulfur atom is particularly preferably a single bond or from 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0. A divalent linking group formed by ~5 sulfur atoms.

In the above, in the case where the divalent linking group has a substituent, the substituent For example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, and an N-sulfonium group are mentioned. Alkoxy groups such as an amine group and an ethoxy group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a halogen atom such as chlorine or bromine; a methoxycarbonyl group and an ethoxy group; Alkoxycarbonyl group having 2 to 7 carbon atoms such as a carbonyl group or a cyclohexyloxycarbonyl group, a carbonate group such as a cyano group or a third butyl carbonate.

In the above formula (1), R ¹ represents a (m+n)-valent linking group. m+n satisfies 3~10.

The (m+n)-valent linking group represented by the above R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0. The group formed by ~20 sulfur atoms may be unsubstituted or more substituted.

Specific examples of the (m+n)-valent linking group represented by the above R ¹ include specific examples (1) to (17) disclosed in paragraphs 0082 and 0083 of JP-A-2007-277514.

In the above formula (1), m represents a positive number of 8 or less. m is preferably from 0.5 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3.

Further, in the above formula (1), n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In the above formula (1), P ¹ represents a polymer chain, and can be selected from known polymers or the like according to the purpose and the like. m P ¹ may be the same or different.

In the polymer, when the polymer chain is formed, it is preferably a polymer or copolymer selected from a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, or a guanamine polymer. An epoxy-based polymer, an anthrone-based polymer, and a modified or copolymer thereof (for example, a copolymer of a polymer comprising a polyether/polyurethane copolymer or a polyether/vinyl monomer) At least one selected from the group consisting of: a random copolymer, a block copolymer, and a graft copolymer, more preferably a polymer or copolymer selected from a vinyl monomer, or an ester system At least one of a group consisting of a polymer, an ether polymer, a urethane polymer, and the like, or a modified or copolymer thereof is preferably a polymer or copolymer of a vinyl monomer.

The polymer chain P ¹ preferably contains at least one repeating unit.

The number k of repetitions of the at least one repeating unit in the polymer chain P ¹ is preferably 3 or more, and more preferably 5 or more, from the viewpoint of exerting a steric repulsive force and improving dispersibility.

In addition, from the viewpoint of suppressing the large volume of the polymer dispersant represented by the above formula (1) and causing the titanium dioxide particles (D) to be densely present in the white cured film, the number of repeating units of the at least one repeating unit is k It is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less.

Further, the above polymer chain is preferably soluble in an organic solvent. If and When the affinity of the organic solvent is low, the affinity with the dispersion medium is weak, and the adsorption layer having sufficient dispersion stabilization cannot be ensured.

Among the polymer dispersants represented by the above formula (1), a polymer dispersant represented by the following formula (2) is preferred.

In the above formula (2), A ² represents a monovalent substituent, and the above monovalent substituent has at least one group selected from the group consisting of an acid group, a urea group, a urethane group. a group, a group containing a coordinating oxygen atom, a group containing a basic nitrogen atom, an alkoxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, a heterocyclic group, an alkoxydecane Base, epoxy group, isocyanate group and hydroxyl group. The n A ^{2 's} may be the same or different.

Further, A ² has the same meaning as the above A ¹ in the above formula (1), and the preferred embodiment is also the same.

In the above formula (2), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. The n R ^{4 's} may be the same or different. In addition, m R ^{5 's} may be the same or different.

The divalent linking group represented by R ⁴ and R ⁵ may be the same as those exemplified as the divalent linking group represented by R ^{2 in} the above formula (1), and the preferred embodiment is also the same.

In the above formula (2), R ³ represents a (m+n)-valent linking group. m+n satisfies 3~10.

The (m+n)-valent linking group represented by R ³ above includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0. The group formed by ~20 sulfur atoms may be unsubstituted or more substituted.

The (m+n)-valent linking group represented by the above R ³ may be the same as those exemplified as the (m+n)-valent linking group represented by R ^{1 of} the above formula (1). The preferred form is also the same.

In the above formula (2), m represents a positive number of 8 or less. m is preferably 0.5 ~5, more preferably 1~4, especially preferably 1~3.

Further, in the above formula (2), n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

Further, P ² in the formula (2) represents a polymer chain, and can be selected from known polymers or the like according to the purpose and the like. m P ² may be the same or different. The preferred form of the polymer is the same as P ¹ in the above formula (1).

In the polymer dispersant represented by the above formula (2), it is preferable that all of R ³ , R ⁴ , R ⁵ , P ² , m and n satisfying the following are satisfied.

R ³ : the above specific example (1), specific example (2), specific example (10), specific example (11), specific example (16) or specific example (17)

R ⁴ : a single bond, or the following structural unit or a combination of the structural units: "1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30" A divalent linking group formed by a hydrogen atom and 0 to 5 sulfur atoms (may also have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, and a phenyl group; a naphthyl group having 6 to 16 carbon atoms such as a aryl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylamino group, an ethoxycarbonyl group and the like, a methoxy group having 1 to 6 carbon atoms, and a methoxy group. An alkoxy group having 1 to 6 carbon atoms such as an ethoxy group, a halogen atom such as chlorine or bromine, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; Base, carbonate ester such as tributyl carbonate, etc.)

R ⁵ : single bond, ethyl group, propyl group, the following group (a) or the following group (b)

Further, in the following group, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, and the like

m:1~3

n: 3~6

The acid value of the polymer dispersant represented by the above formula (1) or (2) is not particularly limited, and from the viewpoint of dispersibility, the acid value is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/ Below g, it is particularly preferably 250 mgKOH/g or less.

In addition, the lower limit of the acid value is not particularly limited, and is preferably 5 mgKOH/g or more, and more preferably 10 mgKOH/g or more from the viewpoint of dispersion stability of the titanium oxide particles.

Here, the acid value of the polymer dispersant represented by the above formula (1) or formula (2) is a solid component acid value.

In the present invention, the acid value of the polymer dispersant represented by the above formula (1) or (2) may be, for example, an acid in the dispersant represented by the above formula (1) or formula (2). The average content of the base is calculated.

The molecular weight of the polymer dispersant represented by the above formula (1) or (2) is preferably from 1,000 to 50,000, more preferably from 3,000 to 30,000, still more preferably from 3,000 to 20,000, in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the effect of introducing a plurality of the adsorption sites introduced into the terminal of the polymer is sufficiently exhibited, and the adsorption property to the surface of the titanium oxide particles is excellent.

Specific examples of the polymer compound represented by the above formula (1) can be referred to the following paragraphs of JP-A-2007-277514, paragraph 0266 (corresponding to U.S. Patent Application Publication No. 2010/0233595 [0389]). The compound C-1 to the compound C-57 synthesized in the examples are incorporated in the specification of the present application.

(Polymer dispersant represented by the above formula (1) or formula (2) resolve resolution)

The polymer dispersant represented by the above formula (1) or (2) is not particularly limited, and can be as described in paragraphs 0114 to 0140 and paragraphs 0266 to 0348 of JP-A-2007-277514. Synthetic methods to synthesize.

The dispersant may also use a resin which will be described below (hereinafter referred to as "minutes" Scattered resin 2"). The dispersion resin 2 is characterized by comprising a repeating unit having a group X (the group X has a pKa of 14 or less) and an oligomer chain or polymer having 40 to 10,000 atoms on the side chain. Chain Y and contains a basic nitrogen atom.

As will be described in detail later, the nitrogen atom and the group X in the dispersion resin 2 have Some of the functional groups having a pKa of 14 or less interact with the titanium oxide particles (D), and further, the dispersion resin 2 has an oligomer chain or a polymer chain Y having an atomic number of 40 to 10,000, and thus, for example, the above oligomer chain Or the polymer chain Y functions as a steric repulsion group, whereby the dispersibility can be exhibited, and the titanium oxide particles (D) can be uniformly dispersed. In addition, even when the composition is stored for a long period of time at room temperature or the like, the oligomer chain or the polymer chain Y interacts with the solvent, whereby the sedimentation of the titanium oxide particles (D) can be suppressed for a long period of time. Further, since the oligomer chain or the polymer chain Y functions as a steric repellency group, thereby preventing aggregation of the titanium oxide particles (D), even if the content of the titanium oxide particles (D) is increased, the dispersion is not easily impaired as described above. Sex and dispersion stability.

Here, the basic nitrogen atom is a basic nitrogen atom, and The dispersion resin 2 preferably has a structure having a nitrogen atom having a pKb of 14 or less, and more preferably a structure having a nitrogen atom having a pKb of 10 or less.

In the present invention, the alkali strength pKb refers to pKb at a water temperature of 25 ° C, and is one of the indexes for quantitatively indicating the strength of the alkali, and has the same meaning as the basicity constant. The alkali strength pKb has a relationship with the acid strength pKa of pKb = 1 - pKa.

The group X having a functional group having a pKa of 14 or less has the same meaning as the group X described below with respect to the dispersion resin 2-1.

The oligomer chain or polymer chain Y having a number of atoms of 40 to 10,000 in the side chain of the dispersion resin 2, and the oligomer chain having 40 to 10,000 atoms as described below with respect to the dispersion resin 2-1 Or the polymer chain Y has the same meaning.

The resin which contains the following repeating unit is a repeating unit containing the group X which has a functional group of pKa of 14 or less, and the repeating unit which has a basic nitrogen atom represented by the following formula. And a repeating unit having an oligomer chain or a polymer chain Y having an atomic number of 40 to 10,000 represented by the following formula (corresponding to the left side of the structure of the repeating unit described below).

In the above formula, x, y and z represent the polymerization molar ratio of the repeating unit, respectively. Preferably, x is 5 to 50, y is 5 to 60, and z is 10 to 90. l represents the number of bonds of the polyester chain, and is an integer of an oligomer chain or a polymer chain which can form an atomic number of 40 to 10,000, preferably 70 to 2,000.

The above dispersion resin 2 is preferably a resin having a structure containing a nitrogen atom (this The repeating unit in which the nitrogen atom is a group X-bonded nitrogen atom having a functional group having a pKa of 14 or less, and the oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain.

The dispersion resin 2 is preferably a resin 2-1 having the following structure (hereinafter referred to as "dispersion resin 2-1" as appropriate): (i) a poly(lower alkylene imine)-based repeating unit, polyallyl a repeating unit containing at least one of a hydroxyl group-based repeating unit, a polydiallylamine-based repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit; And the repeating unit has a group X bonded to the above nitrogen atom and having a functional group having a pKa of 14 or less; and (ii) an oligomer chain or a polymer chain Y of 40 to 10,000 in the side chain .

((i) selected from poly(lower alkylene imine) repeating units, polyallyl a nitrogen atom-containing repeating unit of at least one of an amine-based repeating unit, a polydiallylamine-based repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit)

The dispersion resin 2-1 of the present invention has a repeating unit selected from a poly(lower alkyleneimine) type, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, and a meta-xylenediamine-table The repeating unit (i) containing at least one of a chlorohydrin polycondensate-based repeating unit and a polyvinylamine-based repeating unit containing a nitrogen atom. Thereby, the adsorption force on the surface of the titanium oxide particle (D) is improved, and the interaction between the above-mentioned titanium oxide particles (D) can be reduced.

The poly(lower alkylene imide) may be in the form of a chain or a network.

Will be selected from poly(lower alkylene imine) repeating units, polyallylamine repeats Polymer, polydiallylamine repeating unit, meta-xylenediamine-epichlorohydrin polycondensate repeating unit and polyvinylamine repeating unit, at least one repeating unit containing nitrogen atom (i) The number average molecular weight of the main chain, that is, the portion obtained by removing the above-mentioned oligomer chain or the polymer chain Y portion of the side chain from the dispersion resin 2-1 preferably has a number average molecular weight of 100 to 10,000, more preferably 200. 5,000, the best is 300~2,000. The number average molecular weight of the main chain portion can be determined from the ratio of the terminal group and the hydrogen atom integrated value of the main chain portion measured in the nuclear magnetic resonance spectroscopy, or the amine group-containing oligomer or polymer as a raw material. The molecular weight was measured and determined.

The repeating unit (i) containing a nitrogen atom is particularly preferably a poly(lower alkylene imine) A repeating unit or a polyallylamine-based repeating unit. In the present invention, the lower order of poly(lower alkylene imine) means a carbon number of 1 to 5, and the lower alkylene imide represents an alkylene imine having 1 to 5 carbon atoms. When the structure is clearly illustrated, the dispersion resin 2-1 of the present invention preferably has a structure having a repeating unit represented by the formula (I-1) and a repeating unit represented by the formula (I-2). Or a structure having a repeating unit represented by the formula (II-1) and a repeating unit represented by the formula (II-2).

(repeating unit represented by the formula (I-1) and represented by the formula (I-2) Repeat unit)

The repeating unit represented by the formula (I-1) and the repeating unit represented by the formula (I-2) which are preferred constituent components of the dispersion resin 2-1 of the present invention will be described in detail.

Formula (I-1) Formula (I-2)

In the above formula (I-1) and formula (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group. a independently represents an integer from 1 to 5, respectively. * indicates the connection between the repeating units.

X represents a group having a functional group having a pKa of 14 or less.

Y represents an oligomer chain or a polymer chain having an atomic number of 40 to 10,000.

The dispersion resin 2-1 of the present invention preferably contains a repeating unit represented by the formula (I-1) or a repeating unit represented by the formula (I-3) as a copolymerization unit. ingredient. By using such a repeating unit in combination, the dispersion property of the titanium oxide particles (D) is further improved.

In the above formula (I-3), *, R ¹ , R ² and a have the same meanings as in the formula (I-1).

Y' represents an oligomer chain or a polymer chain having an anion group of 40 to 10,000 atoms.

The repeating unit represented by the above formula (I-3) can be formed by adding a compound having a primary amino group or a secondary amine group to the main chain portion, and having an anti-amine The reaction is carried out by forming an oligomer or polymer of a salt group.

In the formula (I-1), the formula (I-2) and the formula (I-3), R ¹ and R ^{2 are} particularly preferably a hydrogen atom. From the viewpoint of raw material acquisition, a is preferably 2.

The dispersion resin 2-1 of the present invention may contain a lower alkyleneimine as a repeat in addition to the repeating unit represented by the formula (I-1), the formula (I-2) and the formula (I-3). unit. Similarly to the above, the lower alkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms. The dispersion resin 2-1 may contain such a lower alkylene imine repeating unit, or may not contain such a lower alkylene imine repeating unit, and may be dispersed in the case of containing such a lower alkylene imine repeating unit. Among all the repeating units contained in the resin 2-1, the lower alkyleneimine repeating unit preferably contains from 1 mol% to 70 mol%. Further, the nitrogen atom in the repeating unit of the lower alkyleneimine may be further bonded to the group represented by the above X, Y or Y'. Further, a resin containing both a repeating unit to which a group represented by X is bonded and a repeating unit to which Y is bonded in such a main chain structure is also contained in the dispersion resin 2-1.

The repeating unit represented by the formula (I-1) is a repeating unit containing a nitrogen atom which is a nitrogen atom bonded to a group X having a functional group having a pKa of 14 or less, and stores stability and developability. From the viewpoint of the above, in all the repeating units contained in the dispersion resin 2-1, such a repeating unit containing a nitrogen atom preferably contains 1 mol% to 80 mol%.

The repeating unit represented by the formula (I-2) is a repeating unit having an oligomer chain or a polymer chain having an atomic number of 40 to 10,000, and is all of the dispersion resin 2-1 from the viewpoint of storage stability. In the repeating unit, such a repeating unit preferably contains 10 moles. Ear %~90% of the ear.

From the viewpoint of the content ratio of the two, in terms of the balance of dispersion stability and hydrophilicity, the repeating unit (I-1): (I-2) is preferably 10:1 in terms of molar ratio. The range of 1:100.

Further, the repeating unit represented by the formula (I-3) which is used in combination as needed is a partial structure containing an oligomer chain or a polymer chain having an atomic number of 40 to 10,000, and is bonded to the main chain in the form of an ionic bond. The nitrogen atom is preferably contained in an amount of from 0.5 mol% to 20 mol% in terms of the effect of all the repeating units of the dispersion resin 2-1.

(repeating unit represented by the formula (II-1) and repeating unit represented by the formula (II-2))

The repeating unit represented by the formula (II-1) and the repeating unit represented by the formula (II-2) which are preferred constituent components of the dispersion resin 2-1 will be described in detail.

In the general formula (II-1) and the general formula (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. *, X and Y have the same meanings as *, X and Y in the formula (I-1) and the formula (I-2).

The dispersion resin 2-1 is preferably a repeating sheet other than the formula (II-1) In addition to the repeating unit represented by the formula (II-2), the repeating unit represented by the formula (II-3) is further contained as a copolymerization component. By using such a repeating unit in combination, the dispersion property of the titanium oxide particles (D) is further improved.

In the formula (II-3), *, R ³ , R ⁴ , R ⁵ and R ^{6 have the} same meanings as in the formula (II-1). Y' has the same meaning as Y' in the formula (I-3).

In the general formula (II-1), the general formula (II-2) and the general formula (II-3), R ³ , R ⁴ , R ⁵ and R ^{6 are} preferably hydrogen from the viewpoint of availability of raw materials. atom.

The general formula (II-1) is a repeating unit containing a nitrogen atom (a nitrogen atom in which the nitrogen atom is a group X having a functional group having a pKa of 14 or less), and from the viewpoint of storage stability and developability, In all the repeating units contained in the dispersion resin 2-1, such a repeating unit containing a nitrogen atom preferably contains 1 mol% to 80 mol%.

The formula (II-2) is a repeating unit having an oligomer chain or a polymer chain Y having an atomic number of 40 to 10,000, and in terms of storage stability, in all the repeating units of the dispersion resin 2-1, Such a repeating unit preferably contains from 10 mol% to 90 mol%.

Studying the ratio of the two, the dispersion stability and hydrophilicity From the viewpoint of balance, the repeating unit (II-1): (II-2) is preferably in the range of 10:1 to 1:100 in terms of molar ratio.

In all the repeating units of the dispersion resin 2-1, the repeating unit represented by the formula (II-3) which is used in combination as needed preferably contains 0.5 mol% to 20 mol%.

In the dispersion resin 2-1, it is particularly preferable to contain both the repeating unit represented by the formula (I-1) and the repeating unit represented by the formula (I-2) from the viewpoint of dispersibility.

<Group X having a functional group having a pKa of 14 or less>

X has a functional group having a pKa of 14 or less at a water temperature of 25 °C. "The functional group having a pKa of 14 or less" is not particularly limited as long as the physical properties satisfy the above conditions, and the pKa of the known functional group satisfies the above range, and particularly preferably a functional group having a pKa of 12 or less. It is a functional group having a pKa of 11 or less. Specific examples thereof include carboxylic acid (pKa of about 3 to 5), sulfonic acid (pKa of about -3 to 2), -COCH ₂ CO- (pKa of about 8 to 10), and -COCH ₂ CN. (pKa is about 8 to 11), -CONHCO-, phenolic hydroxyl group, -R _F CH ₂ OH or -(R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group, pKa is about 9 to 11), and sulfonamide Amine group (pKa is about 9 to 11) and the like.

The pKa of the functional group possessed by the above-mentioned group X is 14 or less, and the interaction with the above-mentioned titanium oxide particle (D) can be attained.

The group X having a functional group having a pKa of 14 or less is preferably a nitrogen atom directly bonded to the above-mentioned repeating unit containing a nitrogen atom, and the nitrogen atom of the repeating unit containing the nitrogen atom and X can be not only a covalent bond The form is connected, and it can be connected in a form in which a salt is formed by ion bonding.

The group X having a functional group having a pKa of 14 or less of the present invention is preferably a structure represented by the formula (V-1), the formula (V-2) or the formula (V-3).

In the above formula (V-1) and formula (V-2), U represents a single bond or a divalent linking group.

d and e each independently represent 0 or 1.

In the above formula (V-3), Q represents a mercapto group or an alkoxycarbonyl group.

The divalent linking group represented by U may, for example, be an alkylene group (more specifically, for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CHMe-, -(CH ₂ ) ₅ -, - CH ₂ CH(nC ₁₀ H ₂₁ )-etc.), an oxygen-containing alkylene group (more specifically, for example, -CH ₂ OCH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ -, etc.), an aryl group (e.g., stretching phenyl, stretching tolyl, stretching biphenyl, stretching naphthyl, stretching furanyl, pyrrolylene, etc.), alkoxy (e.g., ethoxy, propenoxy, benzene) An oxy group, etc., an alkenyl group (for example, a vinyl group), and the like. Further, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents a mercapto or alkoxycarbonyl group. It is preferable that Q is a mercapto group, and from the viewpoint of availability of a raw material (precursor X of X), it is preferably an ethylene group.

The group X of the present invention is preferably bonded to the above nitrogen atom of a repeating unit containing a nitrogen atom. Thereby, the dispersibility and dispersion of the above titanium oxide particles (D) are stable Qualitatively and dramatically improved.

Further, the group X contains a functional group having a pKa of 14 or less as a Part of the structure, so it also functions as an alkali-soluble group. Thereby, it is considered that the developability of the alkali-developing liquid in the uncured region is improved, and the dispersibility, the dispersion stability, and the developability can be achieved.

The content of the functional group having a pKa of 14 or less in X is not particularly limited. It is preferably 0.01 mmol to 5 mmol with respect to 1 g of the dispersion resin 2. Within this range, the dispersibility and dispersion stability of the titanium dioxide particles (D) are improved, and the developability of the uncured portion is excellent. In addition, it is preferable from the viewpoint of the acid value that the acid value of the dispersion resin 2 is about 5 mgKOH/g to 50 mgKOH/g.

(Opide chain or polymer chain Y with an atomic number of 40 to 10,000)

Y includes a known polymer chain such as polyester, polyamine, polyimine or poly(meth)acrylate which can be bonded to the main chain portion of the dispersion resin 2. The bonding site of Y and the dispersion resin 2 is preferably the terminal of the oligomer chain or the polymer chain Y.

Y is preferably bonded to the above nitrogen atom with at least one repeating unit containing a nitrogen atom selected from the group consisting of poly(lower alkylene imine) repeating units, polyallylamine repeating units, and poly a diallylamine-based repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. a poly(lower alkylene imine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and a main body of at least one of repeating units containing a nitrogen atom, such as a repeating unit of a nitrogen atom The bonding mode of the chain portion and Y is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the bonding mode of Y to the main chain portion is a covalent bond: ion bond = 100:0 to 0:100, preferably 95:5 to 5:95. When it is outside this range, dispersibility and dispersion stability will deteriorate, and solvent solubility will become low.

Y preferably forms an ionic bond in the form of a guanamine bond or a carboxylate with the above nitrogen atom of the above repeating unit containing a nitrogen atom.

The atomic number of the oligomer chain or polymer chain Y is preferably from 50 to 5,000, more preferably from 60 to 3,000, from the viewpoint of dispersibility, dispersion stability, and developability.

When the number of atoms of each of the above oligomer chain or polymer chain Y is less than 40, the graft chain is short, so that the steric repulsion effect is small and the dispersibility is lowered. On the other hand, if the number of atoms of each of the above oligomer chain or polymer chain Y exceeds 10,000, the oligomer chain or polymer chain Y becomes too long, and the adsorption force on the titanium oxide particles (D) may be excessive. Reduced and reduced dispersion.

Further, the number average molecular weight of Y can be measured by a polystyrene equivalent value obtained by a GPC method. The number average molecular weight of Y is particularly preferably from 1,000 to 50,000, and from the viewpoint of dispersibility, dispersion stability, and developability, it is preferably from 1,000 to 30,000.

The side chain structure represented by Y is preferably two or more in one molecule of the resin with respect to the main chain, and is preferably five or more.

More preferably, Y has a structure represented by the formula (III-1).

[化23]

In the general formula (III-1), Z represents a polycondensation having a polyester chain as a partial structure The compound or oligomer represents a residue obtained by removing a carboxyl group from a polyester having a free carboxylic acid represented by the following formula (IV).

In the formula (IV), Z has the same meaning as Z in the formula (III-1).

In the case where the dispersion resin 2-1 contains a repeating unit represented by the formula (I-3) or the formula (II-3), Y' is preferably a formula (III-2).

In the formula (III-2), Z has the same meaning as Z of the formula (III-1).

Polyester having a carboxyl group at a single terminal (polyester represented by the formula (IV)) By (IV-1) polycondensation of a carboxylic acid with a lactone, (IV-2) polycondensation of a hydroxyl group-containing carboxylic acid, (IV-3) a diol with a dicarboxylic acid (or a cyclic acid anhydride) Polycondensation Got it.

(IV-1) The carboxylic acid used in the polycondensation reaction of the carboxylic acid and the lactone is preferably An aliphatic carboxylic acid (a linear or branched carboxylic acid having 1 to 30 carbon atoms). These carboxylic acids may also be used in combination. As the lactone, a known lactone can be used.

These lactones may also be used in combination.

The molar ratio of the addition of the carboxylic acid to the lactone varies depending on the molecular weight of the target polyester chain, and thus cannot be clearly determined. However, it is preferably a carboxylic acid: lactone = 1:1 to 1:1,000, preferably 1:3~1:500.

(IV-2) The hydroxyl group-containing carboxylic acid in the polycondensation of the hydroxyl group-containing carboxylic acid is the same as the hydroxyl group-containing carboxylic acid in the above (IV-1), and the preferred range is also the same.

(IV-3) The diol in the polycondensation reaction of the diol with the dicarboxylic acid (or cyclic acid anhydride) is preferably a linear or branched aliphatic diol (diol having 2 to 30 carbon atoms). .

The dicarboxylic acid is preferably a linear or branched dibasic aliphatic carboxylic acid (a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms).

The dicarboxylic acid and the diol are preferably added in a molar ratio of 1:1. Thereby, a carboxylic acid can be introduced at the end.

The polycondensation in the production of the polyester is preferably carried out by adding a catalyst. The catalyst is preferably a catalyst that functions as a Lewis acid.

The number average molecular weight of the polyester can be measured as a polystyrene-converted value obtained by a GPC method. The polyester has a number average molecular weight of 1,000 to 1,000,000, preferably 2,000 to 100,000, and most preferably 3,000 to 50,000. When the molecular weight is in this range, both dispersibility and developability can be achieved.

The polymer chain-forming polyester in Y from the viewpoint of ease of manufacture Part of the structure is particularly preferably a polyester obtained by polycondensation of (IV-1) a carboxylic acid with a lactone and polycondensation of a (IV-2) hydroxyl group-containing carboxylic acid.

By the specific structure of the repeating unit of the resin and its combination The specific form of the bulk resin 2 [(A-1) to (A-61)] is shown below, but the present invention is not limited thereto. In the following formula, k, l, m and n respectively represent the polymerization molar ratio of the repeating unit, k is 1 to 80, l is 10 to 90, m is 0 to 80, n is 0 to 70, and k + l +m+n=100. p and q represent the number of linkages of the polyester chains, and each independently represents 5 to 100,000. R' represents a hydrogen atom or an alkylcarbonyl group.

[Chem. 26]

[化27]

[化28]

[化29]

[化30]

[化31]

[化32]

[化34]

[化35]

The method of synthesizing the dispersion resin 2 can be synthesized by the method described in Japanese Laid-Open Patent Publication No. 2011-190180.

The dispersion resin 2 of the present invention preferably has a weight average molecular weight of 3,000 to 100,000, more preferably 5,000 to 55,000 as measured by a GPC method. When the molecular weight is in the above range, there is an advantage that high developability and high storage stability can be achieved. Further, the presence of a nitrogen atom in the repeating unit (i) containing a nitrogen atom in the dispersion resin 2 can be confirmed by a method such as acid titration, the presence of a functional group having a pKa of 14 or less, and the functional group and the above repeating unit Nitrate bonding, nuclear magnetic resonance light Spectral method, infrared spectroscopy and other methods to confirm. Further, the aspect in which the (ii) the oligomer chain or the polymer chain Y having 40 to 10,000 atoms in the side chain can be confirmed by a method such as nuclear magnetic resonance spectroscopy or GPC method.

Hereinafter, a specific example of the dispersion resin 2 will be described, and the molecular weight thereof will be described together. R' represents an alkyl group.

[39]

[化42]

(Polymer dispersant represented by the above formula (1) or (2), or a dispersant other than the dispersion resin 2)

The white photosensitive resin composition of the present invention may contain a dispersing agent other than the polymer dispersing agent represented by the above formula (1) or (2) and the dispersing resin 2 (hereinafter referred to as "other dispersing agent" ").

The other dispersing agent which can be used in the present invention is a polymer dispersing agent [for example, a polymer dispersing agent having a phosphorus atom-containing group or an acid group such as a carboxylic acid as an acid-based adsorption site, a polyamine-amine and a salt thereof , polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, change Polyurethane, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, formalin condensate naphthalenesulfonate], and polyoxyalkylene oxide Phosphate, polyoxyethylene ethylamine, alkanolamine, pigment derivative, and the like. In particular, a polymer dispersing agent having at least one of a phosphorus atom-containing group or a carboxylic acid group as an acid-based adsorption site is preferred from the viewpoint of forming a fine pore pattern. Examples of the phosphorus atom-containing group include a phosphate group, a polyphosphate group, a phosphoric acid group and the like.

Other dispersants may be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer depending on the structure thereof.

The other dispersant functions to adsorb on the surface of the titanium dioxide particles to prevent re-agglomeration. Therefore, a terminal modified polymer having a fixed portion on the surface of the titanium oxide particles, a graft polymer, and a block polymer are preferable.

On the other hand, other dispersants have an effect of modifying the surface of the titanium oxide particles, thereby promoting adsorption of the dispersant.

Specific examples of the other dispersing agent include: DISPERBYK 101 (polyamine-amine phosphate) manufactured by BYK Chemie, DISPERBYK 107 (carboxylate) Acid ester), DISPERBYK 110, DISPERBYK 180 (acid-containing copolymer), DISPERBYK 130 (polyamide), Dispa DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 164, DISPERBYK 165, DISPA DISPERBYK 166, DISPERBYK 170 (polymer copolymer), "BYK-P104, BYK-P105 (high molecular weight unsaturated polycarboxylic acid)"; EFKA EFKA 4047, EFKA 4050, EFKA 4010, EFKA 4165 (polyurethane), EFKA ) 4330, Efka (EFKA) 4340 (block copolymer), Efka (EFKA) 4400, Efka (EFKA) 4402 (modified polyacrylate), Efka (EFKA) 5010 (polyester) Indoleamine, EFKA 5765 (high molecular weight polycarboxylate), Efka (EFKA) 6220 (fatty acid polyester), Efka (EFKA) 6745 (phthalocyanine derivative), Evka (EFKA) 6750 (Azo Pigment Derivative)"; Ajisper PB821 and Ajisper PB822 manufactured by Ajinomoto Fine-Techno Co., Ltd.; "Flowlen TG-710 (urethane oligomer)", "Polyflow No. 50E, Polyflow No. 300 (acrylic acid) manufactured by Chemical Company Copolymer)"; Disparlon KS-860, Disparlon, manufactured by Nanben Chemical Co., Ltd. ) 873SN, Disparlon 874, Disparlon #2150 (aliphatic polycarboxylic acid), Disparlon 7004 (polyether ester), Disparlon DA-703-50, Disparlon DA-705, Disparlon DA-725"; Demol RN, Demol N manufactured by Kao Corporation Formalin condensation condensate of naphthalene sulfonate, Demol MS, Demol C, Demol SN-B (aromatic condensate of aromatic sulfonic acid), "Fire Homogenol L-18 (polymer polycarboxylic acid), "Love Wood Emulgen 920, Emulgen 930, Emulgen 935, Emulgen 985 (polyoxyethyl phenyl ether), and Acetamin 86 ( Stearylamine acetate); "SOLSPERSE 5000 (phthalocyanine derivative) manufactured by Lubrizol, SONOSPERSE 22000 (azo pigment derivative) , SONOSPERSE 13240 (polyesteramine), SONOSPERSE 3000, SOLSPERSE 17000, SONOSPERSE 27000 (high at the end of the functional part) Molecular), SONOSPERSE 24000, SOSOLERS 26000, SOLSPERS 28000, SOLSPERS 32000, SOLSPERS 36000, Sonour SOLSPERSE 38500 (grafted polymer), SOLSPERSE 41000"; Nikkor T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemical Co., Ltd. ), MYS-IEX (polyoxy-extension ethyl monostearate) and the like.

In the present invention, SOSOLERS 26000, SOLSPERS 36000 or SOLSPERSE 41000 can be preferably used as a group having a phosphorus atom (for example, a phosphate group or the like). ) A polymer dispersant as an acid-based adsorption site.

In the white photosensitive resin composition of the present invention, the dispersing agent may be used alone or in combination of two or more.

From the viewpoint of dispersibility, the dispersant content of the total solid content of the white photosensitive resin composition of the present invention is preferably from 1% by mass to 40% by mass. The range is more preferably in the range of 1.3% by mass to 30% by mass, further preferably in the range of 1.5% by mass to 20% by mass, particularly preferably in the range of 2% by mass to 10% by mass, and most preferably 2% by mass to 6% by mass. The range of %.

Further, when the white photosensitive resin composition of the present invention contains a dispersing agent, if the dispersing agent is too large, peeling may occur, so that the mass of the dispersing agent in the composition is preferably less than that of the titanium oxide particles (D). The mass ratio of the mass, the dispersant and the titanium dioxide particles (D) in the composition is more preferably the dispersant/titanium dioxide particles (D) = 0.01 to 0.8, and further preferably the dispersant/titanium dioxide particles (D) = 0.03 to 0.5, especially Preferably, the dispersant/titanium dioxide particles (D) = 0.05 to 0.3.

Further, the total content of the binder polymer (A) and the dispersant (sometimes referred to as the polymer content) greatly contributes to the resolution, and in the total solid content of the white photosensitive resin composition, the polymer content is higher. Preferably, the range is from 20% by mass to 50% by mass, more preferably from 25% by mass to 50% by mass, even more preferably from 24% by mass to 46% by mass, particularly preferably from 30% by mass to 46% by mass. . In this case, the binder polymer is preferably a binder polymer having an acid group, and the dispersant is preferably a dispersant having an acidic group and/or a basic group.

When a white cured film having a thickness of 2 μm to 6 μm is formed by using the white photosensitive resin composition of the present invention, a white cured film having a fine pattern such as a pore pattern having a pore diameter of 50 μm or less is formed (viewing degree of viewpoint) In the solid content of the white photosensitive resin composition, the polymer content is preferably 24% by mass to 46% by mass, more preferably 24% by mass to 42% by mass, and still more preferably 30% by mass to 39% by mass. .

Further, when a white cured film having a thickness of 7 μm to 15 μm is formed by using the white photosensitive resin composition of the present invention, the polymer content of the solid component of the white photosensitive resin composition is from the viewpoint of the resolution. It is preferably 24% by mass to 50% by mass, more preferably 30% by mass to 46% by mass, further preferably 35% by mass to 45% by mass, and particularly preferably 39% by mass to 45% by mass.

The present invention also relates to a white photosensitive resin composition comprising (A) a binder polymer, (B) a polymerizable monomer, (C) a polymerization initiator, and (D) an average particle diameter of 100 nm or more. In the solid content of the white photosensitive resin composition, the total content of the binder polymer (A) and the dispersant is 24% by mass to 46% by mass.

According to this embodiment, it is possible to form a white cured film which is particularly excellent in formation of a fine pattern such as a hole pattern having a pore diameter of 50 μm or less.

In the embodiment of the white photosensitive resin composition of the present invention, the preferred range of the total content of the binder polymer (A) and the above dispersant is from the viewpoint of the resolution, and the above binder polymer ( A) is the same as the total content of the above dispersant.

[solvent]

The white photosensitive resin composition of the present invention preferably contains a solvent. The solvent can be constituted using various organic solvents.

The organic solvents usable here are acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetamidine acetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, two Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide , dimethyl hydrazine, γ-butyrolactone, methyl lactate, ethyl lactate, and the like.

These organic solvents may be used singly or in combination. The concentration of the solid content of the white photosensitive resin composition of the present invention is preferably from 2% by mass to 60% by mass.

The white photosensitive resin composition of the present invention may further contain any of the components described in detail below as needed.

[Blue pigment or purple pigment]

The white photosensitive resin composition of the present invention may contain a blue pigment or a violet pigment from the viewpoint of improving the coloring resistance of the white cured film formed by the white photosensitive resin composition of the present invention.

The above blue pigment or violet pigment is preferably one or more selected from the group consisting of Color Index (CI) Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Violet 42 and CI Pigment Blue 1, Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Blue 66, CI Pigment Blue 79, CI Pigment Blue 80.

- Blending of pigments - (color matching)

These organic pigments may be used singly or in combination for the purpose of improving color purity. Specific examples of the above combinations are shown below.

The blue pigment may be used alone as a phthalocyanine-based pigment or may be mixed with a dioxazine-based violet pigment. A preferred example is a mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23.

The quality of the blue pigment and the purple pigment is preferably from 100:0 to 100:100, more preferably less than 100:70.

Preferably, it is dispersed when the blue pigment or the purple pigment is dispersed. Agent. The type of the dispersant is not particularly limited, and a polymer dispersant is preferably used. Examples of polymer dispersants include: DisperBYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106 , DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-163, Despabike (DisperBYK)-164, DisperBYK-166, DisperBYK-167, DisperBYK-168, DisperBYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (above BYK Chemie), Evka ( EFKA) 4010, EFKA 4046, EFKA 4080, EFKA 5010, EFKA 5207, EFKA 5244, EFKA 6745, EFKA 6750, EFKA 7414, EFKA 7462, Efka (EFKA) 7500, EFKA 7570, EFKA 7575, EFKA 7580 (above EFKA Additives), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sannopco) and other polymer dispersants; SOSOLSERSE 3000, SOLSPERSE 5000, SOLSPERSE 9000, SOLSPERSE 12000, SOSOLERSE 13240, Sonupas (Sonopas) SOLSPERSE) 13940, SONOSPERSE 17000, SOLSPERS 24000, SOLSPERS 26000, SOSOLERS 28000, SOSOLERS 32000, cable SOSOLERS 36000, SOLSPERSE 39000, SOLSPERSE 41000, SOLSPERSE 71000, etc. SOSOLERS Separators (Zeneca) )Manufactured by the company; Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adi Copronik (A) Deka Pluronic) L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72, Ai Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Adeka Pronik Pluronic) P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123 ))) Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), "Disparlon" KS-860, Disparlon 873SN, and pedicle Disparlon 874 (polymer dispersant), Disparlon #2150 (aliphatic polycarboxylic acid), Disparlon #7004 (polyether ester type).

In addition, phthalocyanine derivatives (trade name: EFKA-745 (made by EFKA)), SOLSPERS 5000, SONOSPERSE can also be used together. 12000, Solinos (SOLSPERSE) 22000 (made by Zeneca (manufactured by Zeneca)) and other pigment derivatives.

[decane coupling agent]

A decane coupling agent can be used for the white photosensitive resin composition of the present invention from the viewpoint of further improving the adhesion to the substrate.

The decane coupling agent preferably has an alkoxyalkyl group as a hydrolyzable group capable of forming a chemical bond with an inorganic material. Further, it is preferred to have a group which exhibits an affinity with an organic resin or a bond, and it is preferred to have a (meth)acryl fluorenyl group, a phenyl group, a fluorenyl group, or a glycidol. The oxetanyl group is preferably a (meth) acrylonitrile group or a glycidyl group.

That is, the decane coupling agent used in the present invention is preferably a compound having an alkoxyalkyl group, a (meth) acryl fluorenyl group or an epoxy group, and specifically, a structure having the following structure A (meth) acrylonitrile-trimethoxydecane compound, a glycidyl-trimethoxydecane compound, or the like.

Further, the decane coupling agent of the present invention is preferably a decane compound having at least two functional groups having different reactivity in one molecule, and particularly preferably having an amine group and an alkoxy group as a functional group. Such a decane coupling agent is, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane (N-β-aminoethyl-γ-aminopropyl-methyl Dimethoxydecane) (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxydecane (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) : KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxydecane (trade name: KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), γ- Aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903), γ-aminopropyl-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903) Wait.

The amount of addition of the decane coupling agent is preferably from 0.01% by mass to 5.0% by mass, and more preferably from 0.05% by mass to 3.0% by mass, based on the total solid content of the white photosensitive resin composition.

[Anti-Colorant (E)]

The white photosensitive resin composition of the present invention contains a coloring preventive agent (E).

The coloring inhibitor of the present invention is preferably a phenol compound and a phosphite compound or a sulfide compound known as an antioxidant, more preferably a phenol compound having a molecular weight of 500 or more, and a phosphorous acid having a molecular weight of 500 or more. An ester compound or a thioether compound. These compounds may be used in combination of two or more kinds. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. More preferably, it has a substituent at a site adjacent to the phenolic hydroxyl group (ortho), and the substituent in this case is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, more preferably a methyl group. Ethyl, propyl sulfonyl, isopropenyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, octyl, isooctyl, 2-ethylhexyl . Further, a stabilizer having a phenol group and a phosphite group in the same molecule may be mentioned as a preferred raw material.

These compounds are easily available as commercially available products and are sold by the following manufacturers. Asahi Electric Industrial Co., Ltd. as Adekastab AO-50, Adekastab AO-60, Adekastab AO-20, Eddie Costap (Adekastab) AO-70, acquired by Adekastab AO-80.

The content of the coloring inhibitor in the white photosensitive resin composition is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 15% by mass or less, in terms of solid content.

[sensitizer]

In order to increase the radical generating efficiency of the (C) polymerization initiator and to achieve a long wavelength of the photosensitive wavelength, the white photosensitive resin composition of the present invention may contain a sensitizer.

The sensitizer which can be used in the present invention preferably sensitizes the above (C) polymerization initiator by an electron transfer mechanism or an energy shift mechanism.

Examples of the sensitizer include those belonging to the following compounds and having an absorption wavelength in a wavelength range of 300 nm to 450 nm.

The sensitizer is specifically described in the description of paragraphs 0231 to 0253 of the Japanese Patent Application Laid-Open No. 2010-106268 (the corresponding US Patent Application Publication No. 2011/0124824 [0256] to [0273]). Incorporated into the specification of the present application.

The content of the sensitizer in the white photosensitive resin composition is preferably 0.1% by mass or more and 20% by mass or less in terms of solid content, from the viewpoint of the light absorption efficiency in the deep portion and the decomposition efficiency of the initiator. More preferably, it is 0.5 mass% or more and 15 mass% or less.

The sensitizer may be used alone or in combination of two or more.

[common sensitizer]

The white photosensitive resin composition of the present invention preferably further contains a co-sensitizer.

The co-sensitizer of the present invention has an effect of further improving the sensitivity of the (C) polymerization initiator or the sensitizer to actinic radiation or suppressing the inhibition of oxygen on the polymerization of the (B) polymerizable monomer.

For the specific sensitizer, the descriptions of paragraphs 0254 to 0257 of the Japanese Patent Application Laid-Open No. 2010-106268 (the corresponding US Patent Application Publication No. 2011/0124824 [0277] to [0279]), The content is incorporated into the specification of the present application.

The content of the co-sensitizer is preferably 0.1% by mass or more based on the mass of all the solid components of the white photosensitive resin composition, from the viewpoint of improving the curing rate by the balance between the polymerization growth rate and the chain movement. In the range of 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and further preferably 1.5% by mass or more and 20% by mass or less.

[Polymerization inhibitor]

In the present invention, in order to prevent unnecessary polymerization of a compound having a polymerizable ethylenically unsaturated double bond during the production or storage of the white photosensitive resin composition, it is preferred to add a polymerization inhibitor.

Examples of the polymerization inhibitor which can be used in the present invention include a phenolic hydroxyl group-containing compound, an N-oxide compound, a piperidine 1-oxyl radical compound, a pyrrolidine 1-oxy radical compound, and an N-nitrous acid. Base phenylhydroxylamines, diazonium compounds and cationic dyes, sulfur group-containing compounds, nitro group-containing compounds, transition metal compounds such as FeCl ₃ and CuCl ₂ .

A better form is as follows.

The phenolic hydroxyl group-containing compound is preferably selected from the group consisting of hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, and benzene.醌, 4,4-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2, A compound in a group consisting of 6-di-t-butyl-4-methylphenol (BHT), a phenol resin, and a cresol resin.

The N-oxide compound is preferably selected from the group consisting of 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, A compound of the group consisting of 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

The piperidine 1-oxyl radical compound is selected from the group consisting of piperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-oxo-2,2,6, 6-Tetramethylpiperidine 1-oxyl radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-acetamide-2,2,6,6- Tetramethylpiperidine 1-oxyl radical, 4-maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl radical and 4-phosphoniumoxy-2,2,6 a compound of the group consisting of 6-tetramethylpiperidine 1-oxyl radical.

The pyrrolidine 1-oxyl radical compound is preferably a 3-carboxypropoxy radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl radical).

The N-nitrosophenylhydroxylamine is preferably a compound selected from the group consisting of N-nitrosophenylhydroxylamine sulfonium salts and N-nitrosophenylhydroxylamine aluminum salts.

The diazonium compound is preferably selected from the group consisting of hydrogen sulfate from 4-diazophenyldimethylamine, tetrafluoroborate from 4-diazodiphenylamine, and 3-methoxy-4-diazo two. A compound of the group consisting of phenylamine hexafluorophosphate.

Preferred polymerization inhibitors which can be used in the present invention are exemplified below, but the present invention is not limited to these compounds. In addition, examples of the phenolic polymerization inhibitor include the following exemplified compounds (P-1) to exemplified compounds (P-24).

[化45]

[化47]

The amine-based polymerization inhibitors include the following exemplified compounds (N-1) to exemplified compounds (N-7).

[化49]

Examples of the sulfur-based polymerization inhibitor include the following exemplified compounds (S-1) to exemplified compounds (S-5).

(S-1) (C ₁₈ H ₃₇ OCOCH ₂ CH ₂ ) ₂ S (S-2) (C ₁₂ H ₂₅ OCOCH ₂ CH ₂ ) ₂ S (S-3) (C ₁₃ H ₂₇ OCOCH ₂ CH ₂ ) ₂ S (S-4) (C ₁₄ H ₂₉ OCOCH ₂ CH ₂ ) ₂ S (S-5) (CH ₂ OCOCH ₂ CH ₂ SC ₁₂ H ₂₅ ) ₄ C

The phosphite-based polymerization inhibitors include the following exemplified compounds (R-1) to exemplified compounds (R-5).

[化51]

Further, each of the compounds shown below can also be used as a preferred polymerization inhibitor.

Among the above exemplified compounds, hydroquinone or p-methoxyphenol is preferred. Di-t-butyl-p-cresol, biphenyltriol, tert-butyl catechol, benzoquinone, 4,4-thiobis(3-methyl-6-tert-butylphenol), 2 , 2'-methylenebis(4-methyl-6-tert-butylphenol)-like phenolic hydroxyl-containing compound, piperidine 1-oxyl radical compound or 2,2,6,6-tetra Methylpiperidine 1-oxyl radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-hydroxy-2,2,6,6-tetramethylper Pyridine 1-oxyl radical, 4-acetamide-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-maleimide-2,2,6,6-tetramethyl 5-piperidine 1-oxyl radical and 4-phosphoniumoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical piperidine 1-oxygen a radical compound, or an N-nitrosophenylhydroxylamine compound of an N-nitrosophenylhydroxylamine sulfonium salt and an N-nitrosophenylhydroxylamine aluminum salt, more preferably 2, 2, 6, 6-tetramethylpiperidine 1-oxyl radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-hydroxy-2,2,6,6-tetra Methylpiperidine 1-oxyl radical, 4-acetamide-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-maleimide-2,2,6,6 - tetramethylpiperidine 1-oxyl radical and 4-phosphoniumoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical piperidine 1-oxyl radical compound, or N N-nitrosophenylhydroxylamine compound like nitrosophenylhydroxylamine sulfonium salt and N-nitrosophenylhydroxylamine aluminum salt, and further preferably N-nitrosophenylhydroxylamine Salt and N-nitrosophenylhydroxylamine compound like N-nitrosophenylhydroxylamine aluminum salt.

Compared with 100 parts by mass of the (C) polymerization initiator, the polymerization inhibitor is more The amount of addition is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 8 parts by mass or less, and most preferably 0.01 parts by mass or more and 5 parts by mass or less.

By setting it as the above range, the hardening reaction of the non-image portion can be sufficiently suppressed, and the curing reaction of the image portion can be promoted, and the image formability and sensitivity can be improved.

[Surfactant]

From the viewpoint of further improving the coating property, various white surfactants may be added to the white photosensitive resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

In particular, the white photosensitive resin composition of the present invention contains a fluorine-based boundary The surface active agent has a further improved solution property (particularly fluidity) when it is prepared as a coating liquid, so that the uniformity of the coating thickness or the liquid-saving property can be further improved.

In other words, when the film formation is carried out using a coating liquid to which a white photosensitive resin composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered to coat the coating layer. The wettability of the surface is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several micrometers (μm) is formed with a small amount of liquid, a film having a uniform thickness having a small thickness unevenness can be more preferably formed, which is effective in these aspects.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the white photosensitive resin composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac F141. , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above produced by Di Aisheng (DIC)), Fluorad FC430, Fu Fluorad FC431, Fluorad FC171 (above Sumitomo 3M (share)), Shaflon (Surflon) S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Shafu Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above manufactured by Asahi Glass), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA).

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and the like ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate). Etc.), polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl phenyl benzene Base ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, manufactured by BASF), Pluronic L31 , Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1, Pionin D-6512, Pionin D-6414, Pionin D-6112, Pionin D-6115, Pionin D-6120, Pionin D-6131, pie Pionin D-6108-W, Pionin D-6112-W, Pionin D-6115-W, Pionin D-6115-X, Pionin ( Pionin) D-6120-X (bamboo oil) (manufacturing of fat (stock)), SONOSPERSE 20000 (made by Lubrizol Co., Ltd.) and so on.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industries Co., Ltd.), and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). , (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (Kyoeisha Chemicals ( () manufacturing), W001 (Yu Shang (share) manufacturing) and so on.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusei Co., Ltd.).

Examples of the anthrone-based surfactants include: Toray. "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Dongli", manufactured by Dow Corning Toray Co., Ltd. Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Torayone" (Toray Silicone) SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials, Shin-Etsu "KP341", "KF6001", "KF6002" manufactured by Shinetsu Silicon Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie.

The surfactant may be used alone or in combination of two or more.

The white photosensitive resin composition may contain a surfactant or a boundary In the case of the surfactant, when the surfactant is contained, the amount of the surfactant added is preferably from 0.001% by mass to 2.0% by mass, more preferably from 0.005% by mass to 1.0%, based on the total mass of the white photosensitive resin composition. quality%.

[Other additives]

Further, a known additive such as a plasticizer or a fat sensitive agent may be added to the white photosensitive resin composition to improve the physical properties of the cured film.

Plasticizers are, for example, dioctyl phthalate, di-dodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate , dioctyl adipate, dibutyl sebacate, triethylene glyceryl, etc., in the case of using a binder polymer, 10 mass can be added with respect to the total mass of the polymerizable compound and the binder polymer %the following.

[UV absorber]

The white photosensitive resin composition of the present invention may also contain an ultraviolet absorber. The ultraviolet absorber is particularly preferably a compound represented by the following formula (I) which is a conjugated diene compound.

In the above formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² may be the same as each other. Different, but not simultaneously, a hydrogen atom.

Further, R ¹ and R ² may form a cyclic amino group together with a nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include a piperidinyl group, a morpholinyl group, a pyrrolidinyl group, a hexahydroazepino group, a piperazinyl group, and the like.

The above R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group having a substituent constant σ _p value (hereinafter also simply referred to as "σ _p value") of Hammett of 0.20 or more and 1.0 or less. The electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less is preferable. R ³ and R ⁴ may also be bonded to each other to form a ring.

Further, at least one of R ¹ , R ² , R ³ and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may also be a copolymer with other monomers.

The description of the substituent of the ultraviolet absorber represented by the above formula (I) can be referred to in paragraphs 0024 to 0033 of WO2009/123109 (corresponding U.S. Patent Application Publication No. 2011/0039195 [0040] to [0059] The contents are incorporated into the specification of the present application. For a preferred embodiment of the compound represented by the above formula (I), reference is made to the exemplified compound (1) of paragraph 0034 to paragraph 0037 of the specification of WO2009/123109 (corresponding to the specification of [0060] of the corresponding US Patent Application Publication No. 2011/0039195). The description of the exemplified compound (14) is incorporated into the specification of the present application.

The white photosensitive resin composition of the present invention may contain an ultraviolet absorber or may not contain an ultraviolet absorber, and in the case of containing an ultraviolet absorber, The total solid content of the white photosensitive resin composition, the content of the ultraviolet absorber is preferably from 0.1% by mass to 10% by mass, more preferably from 0.1% by mass to 5% by mass, even more preferably from 0.1% by mass to 3% by mass.

Further, in the present invention, the above various ultraviolet absorbers may be used alone or in combination of two or more.

The white photosensitive resin composition of the present invention is preferably filtered by a filter to remove foreign matter or to reduce defects and the like. It is not particularly limited as long as it is a filter used in filtration applications and the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6,6, or a polyolefin resin such as polyethylene or polypropylene (polypropylene) may be used. A filter made of high density, ultra high molecular weight, etc. Among these raw materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the filter is suitably from about 0.2 μm to about 10.0 μm, preferably from about 0.3 μm to about 7.0 μm, and more preferably from about 0.4 μm to about 5.0 μm. By setting it as the range, it is possible to reliably remove the fine foreign matter which is mixed into the dissolved pigment or the like and which hinders the preparation of the uniform and smooth white photosensitive resin composition in the subsequent step.

Different filters can also be combined when using filters. At this time, the filtration by the first filter may be performed only once or twice or more. In the case where two or more filters are combined by using different filters, it is preferred that the pore diameter after the second filtration is larger than the pore diameter of the first filtration. Further, it is also possible to combine the first filters having different pore diameters within the above range. The aperture here can be referred to the nominal value of the filter manufacturer. Commercially available filters are available, for example, from Pall Co., Ltd., Iddobond Advantec Toyo Co., Ltd., Japan's Entegris Co., Ltd. (formerly Japan Microris Co., Ltd.) or Kitazawa Micro Filter Co., Ltd. Select from the filter.

The second filter may be formed using the same material or the like as the first filter described above. The pore diameter of the second filter is suitably from about 0.5 μm to about 7.0 μm, preferably from about 2.5 μm to about 7.0 μm, more preferably from about 4.5 μm to about 6.0 μm. By setting it as the range, it is possible to remove the foreign matter which is mixed in the mixed liquid in a state in which the component particles contained in the mixed liquid remain, and which hinders the preparation of the uniform and smooth white photosensitive resin composition in the subsequent step.

For example, the filtration by the first filter may be carried out only in the dispersion, and after the other components are mixed, the second filtration is performed.

The method for producing the white photosensitive resin composition of the present invention is not particularly limited, and a method for producing a composition generally used can be applied. For example, the white photosensitive resin composition of the present invention can be produced by dispersing the binder polymer (A), the polymerizable monomer (B), the polymerization initiator (C), the titanium oxide particles (D), and the like. The agent, the coloring preventive agent (E), and the solvent are mixed, and are subjected to dispersion treatment using a circulating type dispersing device (bead mill).

<White cured film>

The white photosensitive resin composition of the present invention is not easily colored even when heated at 265 ° C for 15 minutes, and a fine pattern having a pore diameter of 50 μm or less can be formed. Therefore, it can be preferably used for forming a white cured film.

That is, the white photosensitive resin composition of the present invention is preferably used for the formation of a white cured film.

Further, the present invention relates to a white cured film formed using the white photosensitive resin composition of the present invention.

[Method for Producing White Cured Film]

The method for producing a white cured film of the present invention comprises the steps of applying the white photosensitive resin composition onto a substrate by a spray method, a roll coating method, a spin coating method (spin coating method), a bar coating method, or the like. a subsequent first heating step; and then a hardening step of hardening by a second heating and/or exposure at a higher temperature.

The conditions of the first heating step are preferably dried at 70 ° C or higher and 110 ° C or lower for 2 minutes or longer and 4 minutes or shorter.

The film thickness of the white cured film is not particularly limited, and from the viewpoint of obtaining the effect of the present invention more effectively, the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, more preferably 0.5 μm or more and 30 μm or less. Further, it is preferably 0.7 μm or more and 20 μm or less, more preferably 2 μm or more and 20 μm or less, and still more preferably 3 μm or more and 20 μm or less.

<White pattern and its manufacturing method>

Hereinafter, the white pattern of the present invention will be described in detail by a method for producing the same.

The method for producing a white pattern of the present invention comprises the steps of: coating a white photosensitive resin composition of the present invention on a substrate to form a white film; The step of exposing the white film (hereinafter referred to simply as "exposure step"); and the step of developing the white film after exposure to form a white pattern (hereinafter referred to simply as "development step").

In the method for producing a white pattern of the present invention, it is preferred to include a hardening step of hardening the formed white pattern by heating and/or exposure after performing the step of forming a white film, the exposing step, and the developing step.

Specifically, the white photosensitive resin composition of the present invention can be applied onto a substrate directly or via another layer to form a white film (white film forming step), and exposure is performed via a predetermined mask pattern, and only The light-irradiated coating film is partially hardened (exposure step), and development is carried out using a developing solution (developing step), thereby forming a white pattern.

Hereinafter, each step will be described.

[White film forming step]

In the white film forming step, the white photosensitive resin composition of the present invention is applied onto a substrate to form a white film.

Examples of the substrate include an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a transparent conductive film attached to the glass. A photoelectric conversion element substrate used in a solid-state imaging device or the like, for example, a germanium substrate or the like, or a complementary metal oxide semiconductor (CMOS).

Further, on the substrates, an undercoat layer may be provided as needed to improve adhesion to the upper layer, to prevent diffusion of substances, or to planarize the surface of the substrate.

Coating method for coating the white photosensitive resin composition of the present invention on a substrate Applications: Various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, spray coating, and screen printing.

The coating film thickness of the white film is not particularly limited, and is preferably 0.2 μm or more and 50 μm or less, more preferably 0.5 μm or more and 30 μm or less, and further preferably 0.7 μm or more from the viewpoint of resolution and developability. 20 μm or less.

The white photosensitive resin composition applied to the substrate is usually dried at 70 ° C or higher and 110 ° C or lower for 2 minutes or longer and 4 minutes or shorter to form a white film.

[Exposure step]

In the exposure step, the white film formed as described above is exposed through a mask, and only the coating film irradiated with light is partially cured.

The exposure is preferably performed by irradiation of radiation, and radiation which can be used for exposure can preferably use ultraviolet rays such as g-rays, h-rays, and i-rays, and more preferably a high-pressure mercury lamp. The irradiation intensity is preferably ⁵ mJ/cm ² or more and 1500 mJ/cm ² or less, more preferably 10 mJ/cm ² or more and 1200 mJ/cm ² or less, and most preferably 10 mJ/cm ² or more and 1000 mJ/cm ² or less.

[Development Step]

After the exposure step, a development step (preferably an alkali development step) is performed to dissolve the unexposed portion of the light in the exposure step into the alkaline aqueous solution. Thereby, only the photohardened portion remains.

The developing solution used in the developing step is not particularly limited, and for example, an alkaline developing solution or a developing solution containing an organic solvent can be used.

The developer is preferably an organic alkaline developer which does not cause damage to the underlying circuit or the like. The development temperature is usually 20° C. or higher and 30° C. or lower, and the development time is 20 seconds or longer and 90 seconds or shorter.

As the alkaline developing solution, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine; diethylamine and di-n-butyl; Secondary amines such as butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide and tetraethylammonium hydroxide; Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethyl hydroxide Tetraalkylammonium hydroxide such as ammonium, methyltriammonium hydroxide or dibutylammonium hydroxide; trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethyl hydroxide A quaternary ammonium salt such as a benzylammonium salt; an aqueous alkaline solution such as a cyclic amine such as pyrrole or piperidine. Further, an appropriate amount of an alcohol or a surfactant may be added to the aqueous alkaline solution and used. The alkali concentration of the alkaline developer is usually 0.001% by mass to 20% by mass, preferably 0.01% by mass to 10% by mass, more preferably 0.1% by mass to 1% by mass. The pH of the alkaline developer is usually from 10.0 to 15.0. The alkali concentration and pH of the alkaline developer can be suitably prepared and used. The alkaline developing solution can be used, for example, by adding a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like in an appropriate amount.

Further, in the case of using a developer containing such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention does not Limited to these embodiments. In addition, "parts" and "%" are quality standards unless otherwise specified.

Further, in the examples, the acid value was determined by a potential difference method (solvent was tetrahydrofuran/water = 54/6 (volume ratio), and the titration solution was 0.1 N aqueous sodium hydroxide solution (acid value)).

Further, in the measurement of the weight average molecular weight to be described later, HPC-8220GPC (manufactured by Tosoh Corporation) was used as a measuring device, TSK guardcolumn SuperHZ-L was used as a guard column, and TSKgel SuperHZM-M, TSKgel SuperHZ4000, and the like were used. A column in which TSKgel SuperHZ3000 and TSKgel SuperHZ2000 are connected in series is used as a column. The column temperature is set to 40 ° C, and 10 μl of a tetrahydrofuran solution having a sample concentration of 0.1% by mass is injected, and the flow rate of tetrahydrofuran as a dissolution solvent is 0.35 ml per minute. Flow, using a Refractive Index (RI) detection device to detect sample peaks, using a calibration curve made using standard polystyrene.

<Example 1>

[Preparation of Titanium Dioxide Dispersion 1]

For the mixed liquid of the following composition, a super dispersing machine (Ultra Apex Mill) manufactured by Shou Industrial Co., Ltd. was used as a circulating type dispersing device (bead mill), and dispersion treatment was carried out as follows to obtain a titanium oxide dispersion liquid.

~Comment~

. Titanium dioxide (manufactured by Ishihara Industry Co., Ltd., CR-90-2) (purity of 90% or more): 540.00 parts

. Dispersant (A-1) (30% by mass of PGMEA solution): 129.00 parts

. Propylene glycol-1-monomethyl ether-2-acetate (PGMEA): 531.00 parts

In the above formula, n is 14, and the polystyrene-equivalent weight average molecular weight of the dispersing agent (A-1) is 6,400, and the acid value is 80 mgKOH/g.

Further, the dispersion device was operated under the following conditions.

. Bead size: φ0.2mm

. Bead filling rate: 75% by volume

. Weekly speed: 10m/s

. Pump supply: 10kg / h

. Cooling water: tap water

. Bead mill annular passage internal volume: 0.15L

. The amount of the mixture to be dispersed: 1.20 kg

After the start of dispersion, the measurement of the average particle diameter was carried out at intervals of 30 minutes (time passed once).

The average particle diameter decreases with the dispersion time (the number of passes), but the amount of change gradually decreases. The dispersion was terminated at a time when the d50 of the particle size distribution was less than 250 nm and the d90 was less than 350 nm. Furthermore, the average particle diameter of the titanium dioxide particles in the dispersion is 253. Nm.

In this measurement, the average particle diameter of the titanium dioxide particles was set to the number average particle diameter obtained by using Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd.

[Preparation of White Photosensitive Resin Composition 1]

The white photosensitive resin composition of Example 1 was obtained by mixing the respective components so as to have the following composition by using the titanium oxide dispersion liquid obtained above.

~ Composition of white photosensitive resin composition~

. The titanium dioxide dispersion prepared above: 36.67 parts

. The following binder polymer (B-1) 40% by mass PGMEA solution: 31.58 parts

The weight average molecular weight (Mw) was 11,000, and the copolymerization ratio (mol ratio) was as follows.

. Polymerizable monomer (pentaerythritol tetraacrylate): 8.92 parts

(A-TMMT manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; M-1 in the following table)

. Polymerization initiator (K-1): 2.54 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.21 parts

. Decane coupling agent (N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane): 0.04 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (Megafac F-781F manufactured by DiCai (DIC)) 0.2% by mass PGMEA solution: 4.17 parts

. PGMEA: 3.10 servings

. Cyclohexanone: 12.76 parts

<Example 2 to Example 4 and Example 7>

In addition to changing the type of the dispersant, the polymerization initiator, and the binder polymer (the following dispersant (A-2), the following polymerization initiator (K-2), the following polymerization initiator (K-3) The white photosensitive resin compositions of Examples 2 to 4 and Example 7 were prepared in the same manner as in Example 1 except for the following binder polymer (B-2).

Regarding A-2, the weight average molecular weight (Mw) was 9000, and the copolymerization ratio (mol ratio) was as described above.

In the above formula, n is 9, and with respect to B-2, the weight average molecular weight (Mw) is 10,000, and the copolymerization ratio (mole ratio) is as described above.

<Example 5>

[Preparation of Blue Pigment Dispersion]

The blue pigment dispersion liquid (C-1) was obtained by the operation according to the above-described titanium oxide dispersion treatment for the mixed liquid of the following composition.

~Comment~

. C.I. Pigment Blue 15:6:88.80 parts

. C.I. Pigment Violet 23: 23.20 parts

. Dispersant (SOLSPERSE 36000; manufactured by Lubrizol) 30% by mass PGMEA solution: 152.00 parts

. PGMEA: 536.00 servings

[Preparation of White Photosensitive Resin Composition 2]

Using the blue pigment dispersion liquid (C-1) prepared by the above method, each component was mixed so as to have the following composition, and the white photosensitive resin composition of Example 5 was obtained.

~ Composition of white photosensitive resin composition~

. Blue pigment dispersion (C-1) prepared by the above method: 0.03 parts

. Titanium dioxide dispersion prepared in the same manner as in Example 1 : 36.66 parts

. The above adhesive (B-1) 40% by mass PGMEA solution: 31.57 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 8.92 parts

(New Nakamura Chemical Industry Co., Ltd. manufactures A-TMMT; M-1 in the following table)

. The above polymerization initiator (K-2): 2.54 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.21 parts

. Decane coupling agent (N-2-(aminomethyl)-3-aminopropylmethyldimethoxydecane): 0.04 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (manufactured by Dickson (DIC), Megafac F-781F) 0.2% by mass PGMEA solution: 4.17 parts

. PGMEA: 3.10 servings

. Cyclohexanone: 12.75 parts

<Example 6>

A white photosensitive resin composition of Example 6 was prepared in the same manner as in Example 5 except that the type of the blue pigment dispersion liquid was changed to the following blue pigment dispersion liquid (C-2).

In Example 6, a mixed liquid was prepared as follows, and a blue pigment dispersion liquid (C-2) was obtained by an operation according to the above-described titanium oxide dispersion treatment.

~Comment~

. C.I. Pigment Violet 23: 80.00 parts

. Dispersant (SOLSPERSE 36000; manufactured by Lubrizol) 30% by mass PGMEA solution: 232.00 parts

. PGMEA: 488.00 servings

<Example 8>

[Preparation of titanium dioxide dispersion 2]

A dispersion liquid was prepared in the same manner as in Example 1 except that the composition and the amount of the mixed liquid to be subjected to the dispersion treatment were changed as described below.

~Comment~

. Titanium dioxide (manufactured by Ishihara Industry Co., Ltd., CR-90-2) (purity of 90% or more): 272.57 parts

. Dispersant (SOLSPERSE 36000) (30% by mass PGMEA solution): 136.29 parts

. Propylene glycol-1-monomethyl ether-2-acetate (PGMEA): 241.44 parts

. The amount of the mixed solution for dispersion treatment: 0.65 kg

[Preparation of White Photosensitive Resin Composition 3]

The white photosensitive resin composition of Example 8 was obtained by mixing the respective components in such a manner that the titanium dioxide dispersion liquid prepared by the above method was used.

~ Composition of white photosensitive resin composition~

. Titanium dioxide dispersion prepared by the above method: 40.56 parts

. The above binder polymer (B-1) 40% by mass PGMEA solution: 28.35 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 8.92 parts

(New Nakamura Chemical Industry Co., Ltd. manufactures A-TMMT; M-1 in the following table)

. The above polymerization initiator (K-2): 2.54 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.21 parts

. Decane coupling agent (N-2-(aminomethyl)-3-aminopropylmethyldimethoxydecane) 1% by mass solution of cyclohexanone: 4.20 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (manufactured by Dickson (DIC), Megafac F-781F) 0.2% by mass PGMEA solution: 4.17 parts

. PGMEA: 11.04 copies

<Example 9, Example 10>

In addition to changing the type of dispersant to SONOSPERSE 26000, A white photosensitive resin composition was prepared in the same manner as in Example 8 except for SONOSPERSE 41000.

<Example 11>

[Preparation of White Photosensitive Resin Composition 4]

The white photosensitive resin composition of Example 11 was obtained by mixing the components in such a manner as to have the following composition.

~ Composition of white photosensitive resin composition~

. Dispersion prepared in Preparation 2 of titanium dioxide dispersion: 45.63 parts

. The above binder polymer (B-1) 40% by mass PGMEA solution: 42.07 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 5.88 parts

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT; M-1 in the following table)

. Polymerization initiator (K-2): 2.82 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.24 parts

. Decane coupling agent (N-2-(aminomethylethyl)-3-aminopropylmethyldimethoxydecane) (10% cyclohexanone solution): 0.47 parts

. Polymerization inhibitor (p-methoxyphenol): 0.24 parts

. Surfactant (manufactured by Dixon (DIC), Megafac F-781F) 1% by mass PGMEA solution: 0.90 parts

. PGMEA: 1.99 copies

A white cured film was formed using the white photosensitive resin composition thus prepared, and [heat resistance (color difference ΔE ^* ab)], [spectral measurement (transmittance)], and [pattern formability] were evaluated.

[Formation of White Cured Film (Thickness: 4.0 μm)]

The white photosensitive resin compositions of Examples 1 to 11 were applied to a soda glass (75 mm × 75 mm square, thickness: 1.1 mm) by spin coating, and then heated at 100 ° C for 2 minutes on a hot plate. A coating film having a film thickness of 4.0 μm was obtained. The coated film was exposed at 700 mJ/cm ² by an ultrahigh pressure mercury lamp "USH-500BY" manufactured by Ushio Electric Co., Ltd. Further, the film was heated on a hot plate at 200 ° C for 5 minutes to obtain a white cured film (film thickness: 4.0 μm).

[Heat resistance evaluation]

(Spectrophotometry (reflection))

The spectroscopic light L ^* , a ^* , and b ^* of the white cured film formed as described above were measured by Spectro EyeLT (manufactured by Sakata Ink Co., Ltd.). Further, at the time of measurement, the glass on which the white cured film was formed was placed on a black resist-coated table (black table) and measured. The black resist layer of the black stage has an optical density (OD) of 3.5 (transmittance: 0.03%) at 400 nm, 3.2 (transmittance of 0.06) at 550 nm, and 2.5 at 700 nm (transmittance). The reflectance was 0.32%) and the reflectance was 7% at 400 nm to 700 nm. The OD of the black stage was measured by "MCPD-3000" manufactured by Otsuka Electronics Co., Ltd., and the reflectance was a spectrophotometer (SPECTROPHOTOMETER) CM-2600 manufactured by Konica Minolta Co., Ltd. To measure.

The white cured film was heated on a hot plate at 265 ° C for 15 minutes, and the color density of the white cured film after heating was measured in accordance with the above method to calculate a color difference ΔE ^* ab.

[Spectrophotometry (transmittance)]

The spectroscopic (transmittance) of the above-described white cured film was measured by "MCPD-3000" manufactured by Otsuka Electronics Co., Ltd.

[Pattern formation (film thickness: 4.0 μm)]

The white photosensitive resin composition was applied onto a soda glass (100 mm × 100 mm square, thickness: 0.7 mm) by a spin coating method, and then heated at 100 ° C for 2 minutes on a hot plate to obtain a film thickness of 4.00 μm. Coating film. The coating film was exposed at 700 mJ/cm ² through a mask having a plurality of circular patterns having a diameter of 50 μm and 20 μm by an ultrahigh pressure mercury lamp "USH-500BY" manufactured by Oxtail Motor.

It was immersed and developed for 60 seconds at room temperature using an alkaline developer (CD-2060) (manufactured by FUJIFILM Electronic Materials Co., Ltd.), and then purified by a spin shower. The water was rinsed for 20 seconds. Thereafter, the substrate was further washed with pure water, and then the substrate was dried by high-speed rotation to form a hole pattern.

Pattern formation properties were evaluated for the hole patterns having pore diameters of 50 μm and 20 μm, respectively, according to the following evaluation criteria.

Pattern formation:

1. No pattern is formed.

2. There are a lot of residues and the shape of the pattern is poor.

3. There is a little residue, but the shape of the pattern is acceptable.

4. There is a little residue, but the pattern is clearly formed.

5. No residue and clear patterning.

The results are shown in Table 1 below.

As is clear from Table 1, in Examples 1 to 11, the color difference ΔE ^* ab before and after the heat resistance test was 3 or less, and coloring was suppressed, and a hole pattern having a pore diameter of 50 μm or less was satisfactorily formed.

Further, it has been found that by using a polymer dispersant having a group containing a phosphorus atom as an acid-based adsorption site, a pore pattern of 20 μm or less can be favorably formed.

Further, in Example 11, even when the film thickness was increased to 10 μm, the coloration before and after the heat resistance test was small. Further, as is clear from Table 2 to be described later, a hole pattern of 50 μm or less can be favorably formed.

Then, for the white photosensitive trees of the above-described Example 8 and Example 11, The fat composition and the white photosensitive resin compositions of the following Examples 12 to 17 were formed into white cured films having a thickness of 4.0 μm and 10.0 μm, and the pattern formation property was evaluated for the pore pattern.

In addition to changing the content of the white photosensitive composition as described below, Example 8 The white photosensitive resin compositions of Examples 12 to 17 were prepared in the same manner.

<Example 12>

. Dispersion prepared in Preparation 2 of titanium dioxide dispersion: 45.63 parts

. The above binder polymer (B-1) 40% by mass PGMEA solution: 21.39 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 14.15 parts

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT)

. Polymerization initiator (K-2): 2.82 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.23 parts

. Decane coupling agent (N-2-(aminomethylethyl)-3-aminopropylmethyldimethoxydecane) (10% cyclohexanone solution): 0.47 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (manufactured by Dixon (DIC), Megafac F-781F) 1% by mass PGMEA solution: 0.90 parts

. PGMEA: 14.40 copies

<Example 13>

. Dispersion prepared in Preparation 2 of titanium dioxide dispersion: 45.63 parts

. The above binder polymer (B-1) 40% by mass PGMEA solution: 34.17 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 9.04 parts

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT)

. Polymerization initiator (K-2): 2.82 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.23 parts

. Decane coupling agent (N-2-(aminomethylethyl)-3-aminopropylmethyldimethoxydecane) (10% cyclohexanone solution): 0.47 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (manufactured by Dixon (DIC), Megafac F-781F) 1% by mass PGMEA solution: 0.90 parts

. PGMEA: 6.73

<Example 14>

. Dispersion prepared in Preparation 2 of titanium dioxide dispersion: 45.63 parts

. The above binder polymer (B-1) 40% by mass PGMEA solution: 36.70 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 8.03 parts

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT)

. Polymerization initiator (K-2): 2.82 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.23 parts

. Decane coupling agent (N-2-(aminomethylethyl)-3-aminopropylmethyldimethoxydecane) (10% cyclohexanone solution): 0.47 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (manufactured by Dixon (DIC), Megafac F-781F) 1% by mass PGMEA solution: 0.90 parts

. PGMEA: 5.21 servings

<Example 15>

. Dispersion prepared in Preparation 2 of titanium dioxide dispersion: 45.63 parts

. The above binder polymer (B-1) 40% by mass PGMEA solution: 40.29 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 6.61 parts

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT)

. Polymerization initiator (K-2): 2.80 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.24 parts

. Decane coupling agent (N-2-(aminomethylethyl)-3-aminopropylmethyldimethoxydecane) (10% cyclohexanone solution): 0.47 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (manufactured by Dixon (DIC), Megafac F-781F) 1% by mass PGMEA solution: 0.90 parts

. PGMEA: 3.05 servings

<Example 16>

. Dispersion prepared in Preparation 2 of titanium dioxide dispersion: 44.66 parts

. The above binder polymer (B-1) 40% by mass PGMEA solution: 46.05 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 3.80 parts

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT)

. Polymerization initiator (K-2): 2.76 parts

. Anti-coloring agent (made by Adeka), Adekastab AO-80): 0.23 parts

. Decane coupling agent (N-2-(aminomethylethyl)-3-aminopropylmethyldimethoxydecane) (10% cyclohexanone solution): 0.46 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (made by DiCai (DIC), Megafac F-781F) 1% by mass PGMEA solution: 0.92 parts

. PGMEA: 1.11 servings

<Example 17>

. Dispersion prepared in Preparation 2 of titanium dioxide dispersion: 45.63 parts

. The above binder polymer (B-1) 40% by mass PGMEA solution: 42.48 parts

. Polymerizable monomer (pentaerythritol tetraacrylate): 5.93 parts

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT)

. Polymerization initiator (K-2): 2.84 parts

. Decane coupling agent (N-2-(aminomethylethyl)-3-aminopropylmethyldimethoxydecane) (10% cyclohexanone solution): 0.47 parts

. Polymerization inhibitor (p-methoxyphenol): 0.01 parts

. Surfactant (manufactured by Dixon (DIC), Megafac F-781F) 1% by mass PGMEA solution: 0.90 parts

. PGMEA: 1.74

[Formation of white cured film (film thickness: 10.0 μm)]

With respect to the formation of a white cured film having a film thickness of 10.0 μm, a white cured film having a film thickness of 10.0 μm was obtained in addition to a coating film having a film thickness of 10.0 μm, and [formation of a white cured film (film thickness: 4.0 μm) )] A white cured film having a film thickness of 10.0 μm was obtained in the same manner.

[Pattern formation (film thickness: 10.0 μm)]

The white photosensitive resin composition was applied onto a soda glass (100 mm × 100 mm square, thickness: 0.7 mm) by a spin coating method, and then heated at 100 ° C for 2 minutes on a hot plate to obtain a film thickness of 10.0 μm. Coating film. The coating film was exposed at 1000 mJ/cm ² using an ultrahigh pressure mercury lamp "USH-500BY" manufactured by Ushio motor (manufacturing) through a mask having a plurality of circular patterns having a diameter of 50 μm.

Using an alkaline developer (CD-2060) (manufactured by FUJI FILM Electronic Materials Co., Ltd.), it was immersed and developed at room temperature for 30 seconds, and then further rotated with pure water using a rotary shower. Rinse in 20 seconds. Thereafter, the substrate was further washed with pure water, and then the substrate was dried by high-speed rotation to form a hole pattern.

The pattern formation property was evaluated for each of the hole patterns having a pore diameter of 50 μm according to the following evaluation criteria.

Pattern formation:

1. No pattern is formed.

2. There are a lot of residues and the shape of the pattern is poor.

3. There is a little residue, but the shape of the pattern is acceptable.

4. There is a little residue, but the pattern is clearly formed.

5. No residue and clear patterning.

The relationship between the polymer content (the total content of the binder polymer (A) and the dispersant in the solid component) and the resolution of the white photosensitive resin composition of Example 8 and Example 11 to Example 17 is shown in Table 2 below.

[Table 2]

From the eighth embodiment, the eleventh embodiment to the seventeenth embodiment shown in Table 2 above As a result of the white photosensitive resin composition, it was found that the polymer content was 24% by mass to 46% by mass based on the total solid content of the white photosensitive resin composition, and showed good resolution.

Further, when the film thickness is 4 μm, the polymer content is particularly preferably 24% by mass to 42% by mass based on the total solid content of the white photosensitive resin composition. In addition, when the film thickness is 10 μm, the polymer content is from 35% by mass to 45% by mass based on the total solid content of the white photosensitive resin composition, and particularly excellent resolution is exhibited.

Further, it was found that the white photosensitive resin composition of Example 17 containing no anti-coloring agent exhibited good resolution.

Further, the white photosensitive resin composition having the same composition as that of the white photosensitive resin compositions of Example 8 and Examples 12 to 16 except for the absence of the coloring preventive agent, and Example 8 and Example 12 were used. In Example 16, a white cured film was formed in the same manner, and pattern formation was evaluated, and as a result, the polymer content was obtained in white sensitivity. When the total solid content of the resin composition is from 24% by mass to 46% by mass, a good resolution is obtained. When the film thickness is 4 μm, the total amount of the polymer photosensitive resin composition in the white can be obtained. When the solid content is 24% by mass to 42% by mass, a particularly good resolution is obtained, and when the film thickness is 10 μm, the total solid content of the white photosensitive resin composition in the polymer content can be obtained. When it is 35 mass % -45 mass %, it shows the result of the especially favorable resolution.

Claims (26)

A white photosensitive resin composition comprising (A) a binder polymer, (B) a polymerizable monomer, (C) a polymerization initiator, (D) titanium oxide particles having an average particle diameter of 100 nm or more, and (E) a coloring agent, wherein the polymerization initiator (C) is an oxime ester compound represented by the following formula (A), In the above formula (A), R ¹ , R ² and R ³ each independently represent a monovalent substituent. The white photosensitive resin composition according to claim 1, wherein the titanium dioxide (D) has an average particle diameter of 180 nm or more. The white photosensitive resin composition according to the first aspect of the invention, wherein the content of the titanium dioxide (D) in the solid content of the white photosensitive resin composition is 35 mass% or more. The white photosensitive resin composition according to the second aspect of the invention, wherein the content of the titanium dioxide (D) in the solid content of the white photosensitive resin composition is 35 mass% or more. The white photosensitive resin composition according to claim 1, wherein the coloring preventive agent (E) is a phenol compound. The white photosensitive resin composition according to claim 1, wherein the coloring preventive agent (E) is a phenol compound having a substituent in the ortho position of the phenolic hydroxyl group. The white photosensitive resin composition as described in claim 1 of the patent application, In the solid content of the white photosensitive resin composition, the total content of the binder polymer (A) and the dispersant is 24% by mass or more and 46% by mass or less. The white photosensitive resin composition according to claim 4, further comprising a dispersing agent, and the total of the binder polymer (A) and the dispersing agent in the solid component of the white photosensitive resin composition The content is 24% by mass or more and 46% by mass or less. The white photosensitive resin composition according to Item 7 or Item 8, wherein the total content of the binder polymer (A) and the dispersant is the solid content of the white photosensitive resin composition. It is 30% by mass or more and 46% by mass or less. The white photosensitive resin composition according to claim 7 or 8, wherein the dispersing agent is a polymer dispersing agent having an adsorption site. The white photosensitive resin composition according to claim 10, wherein the adsorption site is an acid adsorption site. The white photosensitive resin composition according to claim 11, wherein the acid-based adsorption site is at least one of a phosphorus atom-containing group or a carboxylic acid group. The white photosensitive resin composition according to claim 12, wherein the polymer dispersant is a polymer dispersant having a group containing a phosphorus atom as an acid-based adsorption site, and the polymer dispersant is a polymer dispersant. SOSOPERS 26000, Sonupas 36000 or Sonupas 41000. The white photosensitive resin composition according to claim 10, wherein the polymer dispersant is represented by the following formula (1), In the above formula (1), R ¹ represents a (m+n) valent linking group, R ² represents a single bond or a divalent linking group; A ¹ represents a monovalent substituent, and the above monovalent substituent has at least one selected from the group consisting of a group in the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group containing a basic nitrogen atom, an alkoxycarbonyl group, An alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, a heterocyclic group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group; n of A ¹ and R ² may be the same or different; A positive number of 8 or less is represented, n represents 1 to 9, m+n satisfies 3 to 10, and P ¹ represents a polymer chain; m of P ¹ may be the same or different. The white photosensitive resin composition according to claim 1, wherein the binder polymer (A) contains a monomer having a carboxyl group. The white photosensitive resin composition according to claim 1, wherein the binder polymer (A) contains a monomer having an epoxy group. The white photosensitive resin composition according to claim 1, wherein the binder polymer (A) contains a monomer having a radical polymerizable double bond. The white photosensitive resin composition according to claim 1, wherein the binder polymer (A) contains a monomer component having a compound represented by the following formula (ED). In the above formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. The white photosensitive resin composition according to claim 18, wherein the binder polymer (A) has an acid value of from 50 mgKOH/g to 400 mgKOH/g. The white photosensitive resin composition according to claim 1, which can be formed into a white cured film having a color difference ΔE*ab of 3 or less before and after heating at 265 ° C for 15 minutes. The white photosensitive resin composition according to the first aspect of the invention, which is capable of forming a white cured film having a color difference ΔE*ab of 2 or less before and after heating at 265 ° C for 15 minutes. The white photosensitive resin composition according to the first aspect of the invention, which is capable of forming a white cured film having a pore pattern having a pore diameter of 50 μm or less. A white photosensitive resin composition comprising (A) a binder polymer, (B) a polymerizable monomer, (C) a polymerization initiator, (D) titanium oxide particles having an average particle diameter of 100 nm or more, and a dispersing agent, and In the solid content of the white photosensitive resin composition, the total content of the binder polymer (A) and the dispersant is 24% by mass to 46% by mass, and the polymerization initiator (C) is as follows. An oxime ester compound represented by the formula (A), In the above formula (A), R ¹ , R ² and R ³ each independently represent a monovalent substituent. The white photosensitive resin composition according to claim 23, wherein the total content of the binder polymer (A) and the dispersant is 30% by mass in the solid content of the white photosensitive resin composition. ~46% by mass. A white cured film which is a white cured film formed using the white photosensitive resin composition as described in claim 1 of the patent application. A method for producing a white pattern, comprising the steps of: coating a white photosensitive resin composition according to claim 1 on a substrate to form a white film; and exposing the white film through a mask And a step of developing the exposed white film to form a white pattern.